Atmospheric Chemistry in a Box or a Bag

Abstract

Environmental chambers have proven to be essential for atmospheric photochemistry research. This historical perspective summarizes chamber research characterizing smog. Experiments with volatile organic compounds (VOCs)-nitrogen oxides (NOx) have characterized O3 and aerosol chemistry. These led to the creation and evaluation of complex reaction mechanisms adopted for various applications. Gas-phase photochemistry was initiated and developed using chamber studies. Post-1950s study of photochemical aerosols began using smog chambers. Much of the knowledge about the chemistry of secondary organic aerosols (SOA) derives from chamber studies complemented with specially designed atmospheric studies. Two major findings emerge from post-1990s SOA experiments: (1) photochemical SOAs hypothetically involve hydrocarbons and oxygenates with carbon numbers of 2, and (2) SOA evolves via more than one generation of reactions as condensed material exchanges with the vapor phase during “aging”. These elements combine with multiphase chemistry to yield mechanisms for aerosols. Smog chambers, like all simulators, are limited representations of the atmosphere. Translation to the atmosphere is complicated by constraints in reaction times, container interactions, influence of precursor injections, and background species. Interpretation of kinetics requires integration into atmospheric models addressing the combined effects of precursor emissions, surface exchange, hydrometeor interactions, air motion and sunlight.