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The atmosphere is a heterogeneous system which is rich in potential chemistry. The processes taking place within this system as well as at the interface of its constituents are of immense importance in understanding how the atmosphere in turn can impact the well-being of all living on the surface of earth. Thus, the heterogeneous chemistry of atmospheric aerosols has since long been subjected to extensive scientific investigation, in view of broadening our understanding of this imperative system.
In this study, the heterogeneous interactions of water vapor and gaseous HNO3 on goethite (a-FeOOH), a prominent component of mineral dust aerosol is investigated with quartz crystal microbalance (QCM) measurements and attenuated total reflectance - Fourier transform IR (ATR-FTIR) spectroscopy. Laboratory synthesized goethite samples of varying size (microrods of specific surface area 34 m2/g and nanorods of specific surface area 121 m2/g) were used in order to identify the size dependent interaction of goethite with H2O and HNO3. The study revealed that the exposure of goethite to gas phase H2O and HNO3 results in the uptake of these gases via surface adsorption. Additionally, this novel combined approach of QCM and ATR-FTIR spectroscopy allowed for quantification of the amount of uptake while the spectroscopic data provided information on the speciation of adsorbed products. Thus, with the QCM and spectroscopic data in hand, a precise interpretation of the reactivity as well as its size dependence was sought. In a general sense, the reactivity of a substance is believed to increase with decreasing particle size. The results of this investigation show that in the case of H2O, both microrods and nanorods take up water while the total amount of adsorbed water, when normalized to surface area, is similar for both particle sizes. However, for HNO3, the saturation coverage of total and irreversibly bound HNO3 on microrods was observed to be higher than that on nanorods. With supplementary analysis, this anomalous size effect was attributed to structural features such as the involvement of surface hydroxyl groups in determining the reactivity, which would be subjected to change as a function of particle size. Furthermore, an investigation of the behavior of HNO3 reacted goethite in aqueous media and the uptake of H2O and HNO3 at their mutual presence was carried out such as to better understand the effects of atmospheric processing upon dispersal within the hydrosphere. Further analysis is warranted before arriving at a general conclusion on the size-dependent reactivity of goethite. However, we may argue that goethite containing aerosols may indicate the same pattern of reactivity within the atmosphere as that observed here. Thus, the inference of this investigation proves to be significant in broadening our understanding of this atmosphere as well as the entire biosphere as a whole.