The depletion of SO2 and H2O in and above the clouds of Venus (45–65 km) cannot be explained by known gas-phase chemistry and the observed composition of the atmosphere. We apply a full-atmosphere model of Venus to investigate three potential explanations for the SO2 and H2O depletion: (1) varying the below-cloud water vapor (H2O), (2) varying the below-cloud sulfur dioxide (SO2), and (3) the incorporation of chemical reactions inside the sulfuric acid cloud droplets. We find that increasing the below-cloud H2O to explain the SO2 depletion results in a cloud top that is 20 km too high, above-cloud O2 three orders of magnitude greater than observational upper limits, and no SO above 80 km. The SO2 depletion can be explained by decreasing the below-cloud SO2 to 20 ppm. The depletion of SO2 in the clouds can also be explained by the SO2 dissolving into the clouds, if the droplets contain hydroxide salts. These salts buffer the cloud pH. The amount of salts sufficient to explain the SO2 depletion entails a droplet pH of ∼1 at 50 km. Because sulfuric acid is constantly condensing out into the cloud droplets, there must be a continuous and pervasive flux of salts of ≈10−13 mol cm−2 s−1 driving the cloud droplet chemistry. An atmospheric probe can test both of these explanations by measuring the pH of the cloud droplets and the concentrations of gas-phase SO2 below the clouds.

Photochemistry is a fundamental process of planetary atmospheres that regulates the atmospheric composition and stability1. However, no unambiguous photochemical products have been detected in exoplanet atmospheres so far. Recent observations from the JWST Transiting Exoplanet Community Early Release Science Program2,3 found a spectral absorption feature at 4.05 μm arising from sulfur dioxide (SO2) in the atmosphere of WASP-39b. WASP-39b is a 1.27-Jupiter-radii, Saturn-mass (0.28 MJ) gas giant exoplanet orbiting a Sun-like star with an equilibrium temperature of around 1,100 K (ref. 4). The most plausible way of generating SO2 in such an atmosphere is through photochemical processes5,6. Here we show that the SO2 distribution computed by a suite of photochemical models robustly explains the 4.05-μm spectral feature identified by JWST transmission observations7 with NIRSpec PRISM (2.7σ)8 and G395H (4.5σ)9. SO2 is produced by successive oxidation of sulfur radicals freed when hydrogen sulfide (H2S) is destroyed. The sensitivity of the SO2 feature to the enrichment of the atmosphere by heavy elements (metallicity) suggests that it can be used as a tracer of atmospheric properties, with WASP-39b exhibiting an inferred metallicity of about 10× solar. We further point out that SO2 also shows observable features at ultraviolet and thermal infrared wavelengths not available from the existing observations.

Planetary atmospheres can have three different origins: nebular gas accreted from the protoplanetary disk (primordial); early, syn-accretionary gas release from planetesimal accretion or outgassing during the cooling of a magma ocean (primary); or long-term release of volatiles from the planetary interior for example, through volcanism (secondary). The atmospheres of rocky planets may evolve from primordial/primary to secondary as they undergo significant modification by geological and atmospheric processes, altering the atmosphere's mass fraction and chemical composition. Modification processes include hydrodynamic escape, erosion and volatile addition from impacts, and volcanic outgassing of volatiles from the interior (see Table 1 for references). A more extensive list of processes which can modify planetary atmospheres, and associated literature which has investigated these effects, can be found in Table 1.In this paper series, we focus on secondary atmospheres which form as a result of volcanic outgassing. The chemistry of volcanic gases is dependent on the oxygen fugacity (fO 2 ) of the magma (and likewise the mantle from which the magma was formed, e.g., Burgisser et al., 2015;Gaillard et al., 2015;Ortenzi et al., 2020), surface pressure through volatile solubility in magmas (Gaillard & Scaillet, 2014), and the relative abundance of volatile elements (i.e., H, C, O, S and N) within the magma. The secondary atmospheres of volcanically active rocky planets are therefore inextricably linked to their geological state. This is particularly useful when considering

Compared to the diversity seen in exoplanets, Venus is a veritable astrophysical twin of the Earth; however, its global cloud layer truncates features in transmission spectroscopy, masking its non-Earth-like nature. Observational indicators that can distinguish an exo-Venus from an exo-Earth must therefore survive above the cloud layer. The above-cloud atmosphere is dominated by photochemistry, which depends on the spectrum of the host star and therefore changes between stellar systems. We explore the systematic changes in photochemistry above the clouds of Venus-like exoplanets orbiting K-dwarf or M-dwarf host stars, using a recently validated model of the full Venus atmosphere (0–115 km) and stellar spectra from the Measurements of the Ultraviolet Spectral Characteristics of Low-mass Exoplanetary Systems (MUSCLES) Treasury survey. SO2, OCS, and H2S are key gas species in Venus-like planets that are not present in Earth-like planets, and could therefore act as observational discriminants if their atmospheric abundances are high enough to be detected. We find that SO2, OCS, and H2S all survive above the cloud layer when irradiated by the coolest K dwarf and all seven M dwarfs, whereas these species are heavily photochemically depleted above the clouds of Venus. The production of sulfuric acid molecules that form the cloud layer decreases for decreasing stellar effective temperature. Less steady-state photochemical oxygen and ozone forms with decreasing stellar effective temperature, and the effect of chlorine-catalyzed reaction cycles diminish in favor of HO x and SO x catalyzed cycles. We conclude that trace sulfur gases will be prime observational indicators of Venus-like exoplanets around M-dwarf host stars, potentially capable of distinguishing an exo-Venus from an exo-Earth.

Life in the clouds of Venus, if present in sufficiently high abundance, must be affecting the atmospheric chemistry. It has been proposed that abundant Venusian life could obtain energy from its environment using three possible sulfur energy-metabolisms. These metabolisms raise the possibility of Venus’s enigmatic cloud-layer SO2-depletion being caused by life. We here couple each proposed energy-metabolism to a photochemical-kinetics code and self-consistently predict the composition of Venus’s atmosphere under the scenario that life produces the observed SO2-depletion. Using this photo-bio-chemical kinetics code, we show that all three metabolisms can produce SO2-depletions, but do so by violating other observational constraints on Venus’s atmospheric chemistry. We calculate the maximum possible biomass density of sulfur-metabolising life in the clouds, before violating observational constraints, to be ~10−5 − 10−3 mg m−3. The methods employed are equally applicable to aerial biospheres on Venus-like exoplanets, planets that are optimally poised for atmospheric characterisation in the near future.