Mineral dust particles have photochemical properties that can promote heterogeneous reactions on their surfaces and therefore alter atmospheric composition. Even though dust photocatalytic nature has received significant attention recently, most studies have focused on inorganic trace gases. Here, we investigated how light changes the chemical interactions between butanol and Arizona test dust, a proxy for mineral dust, under atmospheric conditions. Butanol uptake kinetics were measured, exploring the effects of UV light irradiation intensity (0-1.4 mW/cm), relative humidity (0-10%), temperature (283-298 K), and butanol initial concentration (20-55 ppb). The composition of the gas phase was monitored by a high-resolution proton-transfer-reaction mass spectrometer (PTR-ToF-MS) operating in HO mode. Water was observed to play a significant role, initially reducing heterogeneous processing of butanol but enhancing reaction rates once it evaporated. Gas phase products were identified, showing that surface reactions of adsorbed butanol led to the emission of a variety of carbonyl containing compounds. Under actinic light these compounds will photolyze and produce hydroxyl radicals, changing dust processing from a sink of VOC into a source of reactive compounds.
Dicarboxylic acids have low volatilities and hence are present mostly in the particulate phase, including the surface of dust particles. Mineral dust, globally the most emitted aerosol, has photocatalytic properties that can initiate photo-induced heterogeneous chemistry of organic compounds, which is still poorly characterized. We investigated the photochemistry of five dicarboxylic acids (DCA) i.e., succinic (butanedioic) acid, glutaric (pentanedioic) acid, adipic (hexanedioic) acid, pimelic (heptanedioic) acid and suberic (octanedioic) acid on Arizona test dust (ATD) particles upon UV-A light irradiation (0-1.4 mW cm-2). Gas-phase products were monitored by a high-resolution proton-transfer-reaction mass spectrometer (PTR-ToF-MS), and surface sorbed products were extracted and analyzed by ultra-high-performance liquid chromatography coupled to a heated electrospray ionization high-resolution mass spectrometer (UHPLC-HESI-HRMS). Monoacids and aldehydes were the main observed and quantified gaseous products. In contrast, shorter chain DCA and highly oxygenated products were found at the surface of the dust particles. Interestingly, the photochemistry of these DCAs presented an even-odd alternation concerning their heterogeneous reactivity, with odd-numbered carbon diacids being more reactive than their even-numbered homologous ones. We present and discuss a reaction mechanism for the C 4-C 8 DCA heterogeneous photooxidation catalysed by TiO 2 /Fe 2 O 3-rich dust particles. Our results suggest that photochemical processing on dust surfaces should be regarded as a possible efficient pathway for altering their surface properties impacting ice nucleation and cloud condensation properties.
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