Sulfur chemistry in the Venus mesosphere from SO 2 and SO microwave spectra

First measurements of SO2 and SO in the Venus mesosphere (70-100km) are reported. This altitude range is distinctly above the ~60-70km range to which nadir-sounding IR and UV investigations are sensitive. Since July 2004, use of ground-based sub-mm spectroscopy has yielded multiple discoveries. Abundance of each molecule varies strongly on many timescales over the entire sub-Earth Venus hemisphere. Diurnal behavior is evident, with more SO2, and less SO, at night than during the day. Non-diurnal variability is also present, with measured SO2 and SO abundances each changing by up to 2× or more between observations conducted on different dates, but at fixed phase, hence identical sub-Earth Venus local times. Change as large and rapid as a 5σ doubling of SO on a one-week timescale is seen. The sum of SO2 and SO abundances varies by an order of magnitude or more, indicating at least one additional sulfur reservoir must be present, and that it must function as both a sink and source for these molecules. The ratio SO2/SO varies by nearly two orders of magnitude, with both diurnal and non-diurnal components. In contrast to the strong time dependence of molecular abundances, their altitude distributions are temporally invariant, with far more SO2 and SO at 85-100km than at 70-85km. The observed increase of SO2 mixing ratio with altitude requires that the primary SO2 source be upper mesospheric photochemistry, contrary to atmospheric models which assert upward transport as the only source of above-cloud SO2. Abundance of upper mesospheric aerosol, with assumption that it is composed primarily of sulfuric acid, is at least sufficient to provide the maximum gas phase (SO+SO2) sulfur reported in this study. Sulfate aerosol is thus a plausible source of upper mesospheric SO2