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A number of recent studies have shown that iron dissolution in Fe-containing dust aerosol can be linked to source material (mineral or anthropogenic), mineralogy, and iron speciation. All of these factors need to be incorporated into atmospheric chemistry models if these models are to accurately predict the impact of Fe-containing dusts into open ocean waters. In this report, we combine dissolution measurements along with spectroscopy and microscopy to focus on nanoscale size effects in the dissolution of Fe-containing minerals in low-pH environments and the importance of acid type, including HNO3, H2SO4, and HCl, on dissolution. All of these acids are present in the atmosphere, and dust particles have been shown to be associated with nitrate, sulfate, and/or chloride. These measurements are done under light and dark conditions so as to simulate and distinguish between daytime and nighttime atmospheric chemical processing. Both size (nano- versus micron-sized particles) and anion (nitrate, sulfate, and chloride) are found to play significant roles in the dissolution of α-FeOOH under both light and dark conditions. The current study highlights these important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol. [ABSTRACT FROM AUTHOR]

Heterogeneous chemistry of nitrogen dioxide with lead-containing particles is investigated to better understand lead metal mobilization in the environment. In particular, PbO particles, a model lead-containing compound due to its widespread presence as a component of lead paint and as naturally occurring minerals, massicot, and litharge, are exposed to nitrogen dioxide at different relative humidity. X-ray photoelectron spectroscopy (XPS) shows that upon exposure to nitrogen dioxide the surface of PbO particles reacts to form adsorbed nitrates and lead nitrate thin films with the extent of nitrate formation relative humidity dependent. NO2-exposed PbO particles are found to have an increase in the amount of lead that dissolves in aqueous suspensions at circumneutral pH compared to particles not exposed. These results point to the potential importance and impact that heterogeneous chemistry with trace atmospheric gases can have on increasing solubility and therefore the mobilization of heavy metals, such as lead, in the environment. This study also shows that surface intermediates that form, such as adsorbed lead nitrates, can yield higher concentrations of lead in water systems. These water systems can include drinking water, groundwater, estuaries, and lakes. [ABSTRACT FROM AUTHOR]

Under acidic atmospheric conditions, iron leached from atmospheric mineral dust may influence the distribution of bioavailable iron at a global scale. However, the effects of non-Fe-containing minerals on iron dissolution remain unknown. This work describes metal-metal synergistic and antagonistic effects on iron dissolution that go beyond aggregation and ionic strength effects in mineral dust mixtures. In this study, we investigated iron mobilization by proton-promoted dissolution in natural mineral dust samples from the Kalahari Desert (SZ1) and Australian Red Dawn event (RO), along with one iron oxide proxy, hematite. The total iron dissolution in natural dust samples highly corresponds with the respective amount of Ti, rather than their particle sizes or Fe contents. The dust sample with high Ti content, SZ1, also showed a higher fraction of dissolved Fe(II), under dark conditions. These observations are in good agreement with the dissolution data for hematite artificially mixed with metal oxides. Total iron dissolution in hematite, mixed with TiO 2 , is 1.5- and 2-fold higher compared to that of just hematite under dark and light conditions, respectively. However, dissolution of hematite is suppressed when mixed with Al 2 O 3 and CaO. Under dark conditions, furthermore, dissolved Fe(II) fraction is enhanced for hematite when mixed with TiO 2 compared to that of other mixtures or hematite alone. Yet, dissolved Fe(II) is lower in hematite mixed with TiO 2 under light conditions compared to that of hematite alone, suggesting photo-oxidation of Fe(II) by reactive oxygen species, such as OH radicals. [ABSTRACT FROM AUTHOR]