How relevant is it to use mineral proxies to mimic the atmospheric reactivity of natural dust samples? A reactivity study using so2 as probe molecule

Abstract

The experimental investigation of heterogeneous atmospheric processes involving mineral aerosols is extensively performed in the literature using proxy materials. In this work we questioned the validity of using proxies such as Fe2 O3, FeOOH, Al2 O3, MgO, CaO, TiO2, MnO2, SiO2, and CaCO3 to represent the behavior of complex mixtures of minerals, such as natural desert and volcanic dusts. Five volcanic dusts and three desert dusts were compared to a number of metal oxides, commonly used in the literature to mimic the behavior of desert dusts in the ability to form sulfites and sulfates on the surface exposed to SO2 gas. First, all samples were aged at room temperature, atmospheric pressure, under controlled experimental conditions of 175 ppm SO2 for 1 h under 30% of relative humidity. Second, they were extracted with 1% formalin and analyzed by High-Performance Liquid Chromatography (HPLC) to quantify and compare the amount of sulfites and sulfates formed on their surfaces. It was evidenced that under the experimental conditions of this study neither one selected pure oxide nor a mixture of oxides can adequately typify the behavior of complex mixtures of natural minerals. Therefore, to evaluate the real-life impact of natural dust on atmospheric processes it is of vital importance to work directly with the natural samples, both to observe the real effects of desert and volcanic dusts and to evaluate the relevancy of proposed proxies.