Oxalic acid and sulfate salts are major components of aerosol particles. Here, we explore the potential for their respective precursor species, glyoxal and SO 2 , to form atmospheric brown carbon via aqueousphase reactions in a series of bulk aqueous and flow chamber aerosol experiments. In bulk aqueous solutions, UV-and visible-light-absorbing products are observed at pH 3-4 and 5-6, respectively, with small but detectable yields of hydroxyquinone and polyketone products formed, especially at pH 6. Hydroxymethanesulfonate (HMS), C 2 , and C 3 sulfonates are major products detected by electrospray ionization mass spectrometry (ESI-MS) at pH 5. Past studies have assumed that the reaction of formaldehyde and sulfite was the only atmospheric source of HMS. In flow chamber experiments involving sulfite aerosol and gas-phase glyoxal with only 1 min residence times, significant aerosol growth is observed. Rapid brown carbon formation is seen with aqueous aerosol particles at >80% relative humidity (RH). Brown carbon formation slows at 50-60% RH and when the aerosol particles are acidified with sulfuric acid but stops entirely only under dry conditions. This chemistry may therefore contribute to brown carbon production in cloud-processed pollution plumes as oxidizing volatile organic compounds (VOCs) interact with SO 2 and water.

Abstract. Alpha-dicarbonyl compounds are believed to form brown carbon in the atmosphere via reactions with ammonium sulfate (AS) in cloud droplets and aqueous aerosol particles. In this work, brown carbon formation in AS and other aerosol particles was quantified as a function of relative humidity (RH) during exposure to gas-phase glyoxal (GX) in chamber experiments. Under dry conditions (RH < 5 %), solid AS, AS–glycine, and methylammonium sulfate (MeAS) aerosol particles brown within minutes upon exposure to GX, while sodium sulfate particles do not. When GX concentrations decline, browning goes away, demonstrating that this dry browning process is reversible. Declines in aerosol albedo are found to be a function of [GX]2 and are consistent between AS and AS–glycine aerosol. Dry methylammonium sulfate aerosol browns 4 times more than dry AS aerosol, but deliquesced AS aerosol browns much less than dry AS aerosol. Optical measurements at 405, 450, and 530 nm provide an estimated Ångstrom absorbance coefficient of -16±4. This coefficient and the empirical relationship between GX and albedo are used to estimate an upper limit to global radiative forcing by brown carbon formed by 70 ppt GX reacting with AS (+7.6×10-5 W m−2). This quantity is < 1 % of the total radiative forcing by secondary brown carbon but occurs almost entirely in the ultraviolet range.

The composition, sizes and shapes of particles in the clouds of Venus have previously been studied with a variety of in situ and remote sensor measurements. A number of major questions remain unresolved, however, motivating the development of an exploratory mission that will drop a small probe, instrumented with a single-particle autofluorescence nephelometer (AFN), into Venus’s atmosphere. The AFN is specifically designed to address uncertainties associated with the asphericity and complex refractive indices of cloud particles. The AFN projects a collimated, focused, linearly polarized, 440 nm wavelength laser beam through a window of the capsule into the airstream and measures the polarized components of some of the light that is scattered by individual particles that pass through the laser beam. The AFN also measures fluorescence from those particles that contain material that fluoresce when excited at a wavelength of 440 nm and emit at 470–520 nm. Fluorescence is expected from some organic molecules if present in the particles. AFN measurements during probe passage through the Venus clouds are intended to provide constraints on particle number concentration, size, shape, and composition. Hypothesized organics, if present in Venus aerosols, may be detected by the AFN as a precursor to precise identification via future missions. The AFN has been chosen as the primary science instrument for the upcoming Rocket Lab mission to Venus, to search for organic molecules in the cloud particles and constrain the particle composition.