Environmental context. Iron, a limiting nutrient of plankton in the ocean, is deposited to the sea from atmospheric aerosols. In particular, atmospheric acidic conditions promote dissolution of iron from fly ash, a byproduct of coal-fired power plants. Here, we report that the iron leached from fly ash depends on its source region, and that the type of combustion process may influence the iron species mobilized.Abstract. Fly ash, an iron-containing by-product of coal-fired power plants, has been observed in atmospheric aerosol plumes. Under the acidic atmospheric conditions resulting from the uptake of atmospheric gases, iron leached from fly ash can impact global biogeochemical cycles. However, the fly ash source region, as well as its generating power plant, plays an important role in the amount, speciation and lability of iron. Yet no comparative studies have been made on iron leached from fly ash from different sources. This study reports the iron mobilisation by proton-promoted dissolution from wellcharacterised fly ash samples from three distinctive locations: the USA Midwest, north-east India and Europe. In addition, pH dependency was also investigated. Proton-promoted dissolution showed a variability between source regions with a relative iron leach in the order USA Midwestern . north-east Indian . European ash. In addition, the initial rate of iron leach suggests that source region is indeed a determining factor in the iron leaching capacity of fly ash, because dissolution from Midwestern fly ash is also faster than both European and Indian ash. Finally, the combustion process of fly ash proved to be significant for the iron speciation, given that well-combusted fly ash samples leached mostly Fe 3þ rather than bioavailable Fe 2þ . The role of fly ash should therefore be taken into account in order to better understand the effects of combustion particles in atmospheric iron deposition.

Atmospheric combustion particles, such as fly ash emitted from coal-fired power plants, are a potential source of atmospheric iron, with significant implications in climate and global biogeochemical cycles. While the iron content and speciation of fly ash depend closely on the source region and combustion process, few studies have been carried out comparing the atmospheric processing of fly ash produced from coal-fired power plants in different regions. In this study, we present an investigation of iron dissolution in acidic aqueous solutions: HNO 3 and HCl at pH 1 and pH 2 under daytime and nighttime conditions for three fly ash samples from three different sources: United States (USFA), Central Europe (EUFA), and India fly ash (INFA). Iron mobility and speciation depend on the source region and the combustion efficiency that generates fly ash. In HCl suspensions, proton-promoted mechanisms lead to larger fractions of aqueous-phase iron leached from fly ash particles, with poorly combusted samples providing significant fractions of Fe 2+ . In HNO 3 suspensions, a surface-mediated redox reaction suppresses the mobility of Fe 2+ , leading to the formation of nitrites. In the presence of solar radiation, previously unrecognized pathways of atmospheric processing enhance the formation Fe 2+ and nitrous acid from combustion particles. The information provided herein could be significant to increase our understanding of the effects of combustion particles in the atmospheric chemical balance regarding iron and nitrites.

Nitric acid, a well-known sink of NO gases in the atmosphere, has been found to be photoactive while adsorbed on tropospheric particles. When adsorbed onto semiconductive metal oxides, nitrate's photochemical degradation can be interpreted as a photocatalytic process. Yet, the photolysis of nitrate ions on the surface of aerosols can also be initiated by changes in the symmetry of the ion upon adsorption. In this study, we use quantum chemistry to model the vibrational spectra of adsorbed nitrate on TiO, a semiconductor component of atmospheric aerosols, and determine the kinetics of the heterogeneous photochemical degradation of nitrate under simulated solar light. Frequencies and geometry calculations suggest that the symmetry of chemisorbed nitrate ion depends strongly on coadsorbed water, with water changing the reactive surface of TiO. Upon irradiation, surface nitrate undergoes photolysis to yield nitrogen-containing gaseous products including NO, NO, HONO, and NO, in proportions that depend on relative humidity (RH). In addition, the heterogeneous photochemistry rate constant decreases an order of magnitude, from (5.7 ± 0.1) × 10 s on a dry surface to (7.1 ± 0.8) × 10 s when nitrate is coadsorbed with water above monolayer coverage. Little is known about the roles of coadsorbed water on the heterogeneous photochemistry of nitrates on TiO, along with its impact on the chemical balance of the atmosphere. This work discusses the roles of water in the photolysis of surface nitrates on TiO and the concomitant renoxification of the atmosphere.

Microspectroscopic analyses of glass surfaces following a single day of cooking events reveal organic depositions that can be traced back to emission sources and airborne distributions.

The effects of atmospheric aging on single-particle nascent sea spray aerosol (nSSA) physicochemical properties, such as morphology, composition, phase state, and water uptake, are important to understanding their impacts on the Earth’s climate. The present study investigates these properties by focusing on the aged SSA (size range of 0.1–0.6 μm) and comparing with a similar size range nSSA, both generated at a peak of a phytoplankton bloom during a mesocosm study. The aged SSAs were generated by exposing nSSA to OH radicals with exposures equivalent to 4–5 days of atmospheric aging. Complementary filter-based thermal optical analysis, atomic force microscopy (AFM), and AFM photothermal infrared spectroscopy were utilized. Both nSSA and aged SSA showed an increase in the organic mass fraction with decreasing particle sizes. In addition, aging results in a further increase of the organic mass fraction, which can be attributed to new particle formation and oxidation of volatile organic compounds followed by condensation on pre-existing particles. The results are consistent with single-particle measurements that showed a relative increase in the abundance of aged SSA core–shells with significantly higher organic coating thickness, relative to nSSA. Increased hygroscopicity was observed for aged SSA core–shells, which had more oxygenated organic species. Rounded nSSA and aged SSA had similar hygroscopicity and no apparent changes in the composition. The observed changes in aged SSA physicochemical properties showed a significant size-dependence and particle-to-particle variability. Overall, results showed that the atmospheric aging can significantly influence the nSSA physicochemical properties, thus altering the SSA effects on the climate.