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.

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.

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