Reactive Oxygen Species Formed by Secondary Organic Aerosols in Water and Surrogate Lung Fluid.

Reactive oxygen species (ROS) play a central role in adverse health effects of air pollutants. Respiratory deposition of fine air particulate matter can lead to the formation of ROS in epithelial lining fluid, potentially causing oxidative stress and inflammation. Secondary organic aerosols (SOA) account for a large fraction of fine particulate matter, but their role in adverse health effects is unclear. Here, we quantify and compare the ROS yields and oxidative potential of isoprene, ß-pinene, and naphthalene SOA in water and surrogate lung fluid (SLF). In pure water, isoprene and ß-pinene SOA were found to produce mainly OH and organic radicals, whereas naphthalene SOA produced mainly H2O2 and O2•-. The total molar yields of ROS of isoprene and ß-pinene SOA were 11.8% and 8.2% in water and decreased to 8.5% and 5.2% in SLF, which can be attributed to ROS removal by lung antioxidants. A positive correlation between the total peroxide concentration and ROS yield suggests that organic (hydro)peroxides may play an important role in ROS formation from biogenic SOA. The total molar ROS yields of naphthalene SOA was 1.7% in water and increased to 11.3% in SLF. This strong increase is likely due to redox reaction cycles involving environmentally persistent free radicals (EPFR) or semiquinones, antioxidants, and oxygen, which may promote the formation of H2O2 and the adverse health effects of anthropogenic SOA from aromatic precursors.

Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (<3) conditions. ROS formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H2O2 with Fe2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H2O2 and Fe2+. In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

Heterogeneous OH Oxidation, Shielding Effects, and Implications for the Atmospheric Fate of Terbuthylazine and Other Pesticides.

Terbuthylazine (TBA) is a widely used herbicide, and its heterogeneous reaction with OH radicals is important for assessing its potential to undergo atmospheric long-range transport and to affect the environment and public health. The apparent reaction rate coefficients obtained in different experimental investigations, however, vary by orders of magnitude depending on the applied experimental techniques and conditions. In this study, we used a kinetic multilayer model of aerosol chemistry with reversible surface adsorption and bulk diffusion (KM-SUB) in combination with a Monte Carlo genetic algorithm to simulate the measured decay rates of TBA. Two experimental data sets available from different studies can be described with a consistent set of kinetic parameters resolving the interplay of chemical reaction, mass transport, and shielding effects. Our study suggests that mass transport and shielding effects can substantially extend the atmospheric lifetime of reactive pesticides from a few days to weeks, with strong implications for long-range transport and potential health effects of these substances.

Products and mechanisms of the heterogeneous reactions of ozone with commonly used pyrethroids in the atmosphere.

The heterogeneous reactions of gas-phase ozone and two pyrethroid pesticides, deltamethrin and permethrin, which are the most frequently applied insecticides today, has been investigated. Tentative identifications of heterogeneous ozonolysis products of both pesticides reveal that the reaction mechanisms differ and are mainly influenced by the presence of the cyano moiety at the α-position of deltamethrin (pyrethroid type II). The mechanism study also suggests the important role of water. Finally, several of the degradation products emerged from the ozonolysis of deltamethrin and permethrin may pose further health and environmental hazard due to their higher toxicity, such as phosgene for permethrin, and bromophosgene, 3-phenoxybenzaldehyde (3-PBA) and fulminic acid for deltamethrin. The results obtained in this study can contribute to better describe the atmospheric fate of pesticides in the particle phase.

The persistence of pesticides in atmospheric particulate phase: An emerging air quality issue.

The persistent organic pollutants (POPs) due to their physicochemical properties can be widely spread all over the globe; as such they represent a serious threat to both humans and wildlife. According to Stockholm convention out of 24 officially recognized POPs, 16 are pesticides. The atmospheric life times of pesticides, up to now were estimated based on their gas-phase reactivity. It has been only speculated that sorption to aerosol particles may increase significantly the half-lives of pesticides in the atmosphere. The results presented here challenge the current view of the half-lives of pesticides in the lower boundary layer of the atmosphere and their impact on air quality and human health. We demonstrate that semivolatile pesticides which are mostly adsorbed on atmospheric aerosol particles are very persistent with respect to the highly reactive hydroxyl radicals (OH) that is the self-cleaning agent of the atmosphere. The half-lives in particulate phase of difenoconazole, tetraconazole, fipronil, oxadiazon, deltamethrin, cyprodinil, permethrin, and pendimethalin are in order of several days and even higher than one month, implying that these pesticides can be transported over long distances, reaching the remote regions all over the world; hence these pesticides shall be further evaluated prior to be confirmed as POPs.