Major Regional-Scale Production of O3 and Secondary Organic Aerosol in Remote Amazon Regions from the Dynamics and Photochemistry of Urban and Forest Emissions.

The Amazon rainforest suffers increasing pressure from anthropogenic activities. A key aspect not fully understood is how anthropogenic atmospheric emissions within the basin interact with biogenic emissions and impact the forest's atmosphere and biosphere. We combine a high-resolution atmospheric chemical transport model with an improved emissions inventory and in-situ measurements to investigate a surprisingly high concentration of ozone (O3) and secondary organic aerosol (SOA) 150-200 km downwind of Manaus city in an otherwise pristine forested region. We show that atmospheric dynamics and photochemistry determine a gross production of secondary pollutants seen in the simulation. After sunrise, the erosion of the nocturnal boundary layer mixes natural forest emissions, rich in biogenic volatile organic compounds, with a lofted pollution layer transported overnight, rich in nitrogen oxides and formaldehyde. As a result, O3 and SOA concentrations greater than ∼47 ppbv and 1.8 µg m-3, respectively, were found, with maximum concentrations occurring at 2 pm LT, 150-200 km downwind of Manaus city. These high concentrations affect a large primary forested area of about 11,250 km2. These oxidative areas are under a NOx-limited regime so that changes in NOx emissions from Manaus have a significant impact on O3 and SOA production.

Kinetics and Product Formation during the Photooxidation of Butanol on Atmospheric Mineral Dust.

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/cm2), 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 H3O+ 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.

Photocatalytic oxidation of selected gas-phase VOCs using UV light, TiO2, and TiO2/Pd.

Heterogeneous photocatalytic oxidation systems using titanium dioxide (TiO2) have been extensively studied for the removal of several volatile organic compounds (VOCs). The addition of noble metals such as palladium on TiO2 may improve photocatalytic activity by increasing charge separation efficiency. In this work, palladium was impregnated on TiO2 and the efficiency of the new catalyst was tested and compared with that of pure TiO2. Pd was impregnated on TiO2 by the reduction method, using NaBH4, and was characterized by XRD, XPS, UV-Vis, and H2 chemisorption. The photocatalytic tests were performed in an annular coated-wall reactor using octane, isooctane, n-hexane, and cyclohexane at inlet concentrations varying from 100 to 120 ppmv. Compared with pure TiO2 film, the photocatalytic activity of TiO2 impregnated with 1 wt% of palladium was improved. All the aforementioned analytical techniques confirmed the presence of Pd incorporated into the structure of TiO2, and the conversion rates were studied in a broad range of residence times, yielding up to 90 % or higher rates in 40 s of residence time, thus underscoring the relevant contribution of the technology.