Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

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The formation, properties and impact of secondary organic aerosol: current and emerging issues

Tropospheric air pollution has impacts on scales ranging from local to global. Reactive intermediates in the oxidation of mixtures of volatile organic compounds (VOCs) and oxides of nitrogen (NOx) play central roles: the hydroxyl radical (OH), during the day; the nitrate radical (NO3), at night; and ozone (O3), which contributes during the day and night. Halogen atoms can also play a role during the day. Here the implications of the complex VOC-NOx chemistry for O3 control are discussed. In addition, OH, NO3, and O3 are shown to play a central role in the formation and fate of airborne toxic chemicals, mutagenic polycyclic aromatic hydrocarbons, and fine particles.

https://science.sciencemag.org/content/sci/276/5315/1045.full.pdf

Tropospheric air pollution: ozone, airborne toxics, polycyclic aromatic hydrocarbons, and particles.

A review has been written to assess the sources, fate and behavior of polycyclic aromatic hydrocarbons (PAH) in the atmosphere. PAH are formed mainly by anthropogenic processes, especially the combustion of organic fuels. PAH concentration in air will reflect the location of source emitters, with high concentrations corresponding with urban and industrial areas. PAH are however ubiquitous contaminants of the environment having been detected in remote areas of the world. This is thought to be due to long term transport in the atmosphere. PAH can also be subjected to chemical and/ or photochemical change whilst resident in the atmosphere prior to their removal by either wet or dry deposition.

A review of atmospheric polycyclic aromatic hydrocarbons : sources, fate and behavior

Quantification of urban organic aerosols at a molecular level: Identification, abundance and seasonal variation

Nitroaromatic compounds are released into the biosphere almost exclusively from anthropogenic sources. Some compounds are produced by incomplete combustion of fossil fuels; others are used as synthetic intermediates, dyes, pesticides, and explosives. Recent research revealed a number of microbial systems capable of transforming or biodegrading nitroaromatic compounds. Anaerobic bacteria can reduce the nitro group via nitroso and hydroxylamino intermediates to the corresponding amines. Isolates of Desulfovibrio spp. can use nitroaromatic compounds as their source of nitrogen. They can also reduce 2,4,6-trinitrotoluene to 2,4,6-triaminotoluene. Several strains of Clostridium can catalyze a similar reduction and also seem to be able to degrade the molecule to small aliphatic acids. Anaerobic systems have been demonstrated to destroy munitions and pesticides in soil. Fungi can extensively degrade or mineralize a variety of nitroaromatic compounds. For example, Phanerochaete chrysosporium mineralizes 2,4-dinitrotoluene and 2,4,6-trinitrotoluene and shows promise as the basis for bioremediation strategies. The anaerobic bacteria and the fungi mentioned above mostly transform nitroaromatic compounds via fortuitous reactions. In contrast, a number of nitroaromatic compounds can serve as growth substrates for aerobic bacteria. Removal or productive metabolism of nitro groups can be accomplished by four different strategies. (a) Some bacteria can reduce the aromatic ring of dinitro and trinitro compounds by the addition of a hydride ion to form a hydride-Meisenheimer complex, which subsequently rearomatizes with the elimination of nitrite. (b) Monooxygenase enzymes can add a single oxygen atom and eliminate the nitro group from nitrophenols. (c) Dioxygenase enzymes can insert two hydroxyl groups into the aromatic ring and precipitate the spontaneous elimination of the nitro group from a variety of nitroaromatic compounds. (d) Reduction of the nitro group to the corresponding hydroxylamine is the initial reaction in the productive metabolism of nitrobenzene, 4-nitrotoluene, and 4-nitrobenzoate. The hydroxylamines undergo enzyme-catalyzed rearrangements to hydroxylated compounds that are substrates for ring-fission reactions. Potential applications of the above reactions include not only the biodegradation of environmental contaminants, but also biocatalysis and synthesis of valuable organic molecules.

Biodegradation of Nitroaromatic Compounds

Directly active mutagens are formed on exposure of the promutagen benzo[a]pyrene to gaseous pollutants in smog. In simulated atmospheres containing 1 part per million nitrogen dioxide and traces of nitric acid, directly mutagenic nitro derivatives are readily formed from both benzo[a]pyrene and perylene, a non-mutagen in the Ames reversion assay. Possible formation of direct mutagens by such reactions on sample collection filters, in exhaust effluents, and in the atmosphere should be recognized.

https://science.sciencemag.org/content/sci/202/4367/515.full.pdf

Atmospheric reactions of polycyclic aromatic hydrocarbons: facile formation of mutagenic nitro derivatives.

Photooxidation of aliphatic amines under simulated atmospheric conditions: formation of nitrosamines, nitramines, amides, and photochemical oxidant

A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation

Real-time and integrated measurements of gaseous and particulate pollutants were conducted inside five conventional diesel school buses, a diesel bus with a particulate trap, and a bus powered by compressed natural gas (CNG) to determine the range of children's exposures during school bus commutes and conditions leading to high exposures. Measurements were made during 24 morning and afternoon commutes on two Los Angeles Unified School District bus routes from South to West Los Angeles, with seven additional runs on a rural/suburban route, and three runs to test the effect of window position. For these commutes, the mean concentrations of diesel vehicle-related pollutants ranged from 0.9 to 19 microg/m(3) for black carbon, 23 to 400 ng/m(3) for particle-bound polycyclic aromatic hydrocarbon (PB-PAH), and 64 to 220 microg/m(3) for NO(2). Concentrations of benzene and formaldehyde ranged from 0.1 to 11 microg/m(3) and 0.3 to 5 microg/m(3), respectively. The highest real-time concentrations of black carbon, PB-PAH and NO(2) inside the buses were 52 microg/m(3), 2000 ng/m(3), and 370 microg/m(3), respectively. These pollutants were significantly higher inside conventional diesel buses compared to the CNG bus, although formaldehyde concentrations were higher inside the CNG bus. Mean black carbon, PB-PAH, benzene and formaldehyde concentrations were higher when the windows were closed, compared with partially open, in part, due to intrusion of the bus's own exhaust into the bus cabin, as demonstrated through the use of a tracer gas added to each bus's exhaust. These same pollutants tended to be higher on urban routes compared to the rural/suburban route, and substantially higher inside the bus cabins compared to ambient measurements. Mean concentrations of pollutants with substantial secondary formation, such as PM(2.5), showed smaller differences between open and closed window conditions and between bus routes. Type of bus, traffic congestion levels, and encounters with other diesel vehicles contributed to high exposure variability between runs.

Dennis R. Fitz

Papers

Atmospheric reactions of polycyclic aromatic hydrocarbons: facile formation of mutagenic nitro derivatives.

Photooxidation of aliphatic amines under simulated atmospheric conditions: formation of nitrosamines, nitramines, amides, and photochemical oxidant

A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation

Characterizing the range of children's air pollutant exposure during school bus commutes.

Measuring self-pollution in school buses using a tracer gas technique