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

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.

Atmospheric formation and fates of toxic ambient air pollutants.

Concentrations of de novo toxicants in ambient air are typically in the ppb range, compared to ppm for occupational exposures. Despite this, some species such as ozone, alone or in combination with other pollutants, have significant health impacts, especially on populations such as children, the elderly, and asthmatics. Reaction products in the atmosphere include gases such as ozone and nitric acid, as well as polar organic species such as aldehydes, acids, hydroperoxides, and peroxides. A brief discussion of indoor vs outdoor levels of several acids/toxicants is included. Emphasis is on homogeneous, gas-phase processes with some examples of gas/solid heterogeneous processes. A brief discussion is included on the role of chlorofluorocarbons in the catalytic destruction of stratospheric ozone in the context of the resulting expected increase in ultraviolet radiation at the earth's surface.

Ubiquitous occurrence of 2-nitrofluoranthene and 2-nitropyrene in air.

Several nitrated polycyclic aromatic hydrocarbons (nitro-PAH) are direct-acting mutagens and/or carcinogens, and are important constituents of combustion emissions and ambient air. These nitro-PAH are emitted from various combustion sources including gasoline and diesel engine exhaust, aluminium smelting effluent, coal fly ash, wood smoke, and cigarette smoke condensates. Of these, diesel engine exhaust is the best characterized, more than 50 nitrated polycyclic aromatic compounds having been identified by Paputa-Peck et al., including 1-nitropyrene (1-NP) as the single most abundant nitro-PAH. However, nitro-PAH may also be formed during source-receptor transport by atmospheric reactions of adsorbed or gas-phase PAH with oxides of nitrogen, nitric acid and other atmospherically important species such as the OH radical. Evidence for the atmospheric formation of nitro-PAH has come only recently, from observations that 2-nitropyrene (2-NP) and 2-nitrofluoranthene (2-NF) neither of which has been reported to be emitted from combustion sources, are among the major nitro-PAH present in ambient air. We present here data from several locations which demonstrate that these two atmospherically formed nitro-PAH are ubiquitous in tropospheric ambient air.

Gaseous nitrate radical: possible nighttime atmospheric sink for biogenic organic compounds.

The gaseous nitrate (NO(3)) radical, which has recently been measured in nighttime ambient atmospheres over the United States and Europe at concentrations up to approximately 350 parts per trillion, has now been shown to react rapidly with the biogenically emitted organic compounds dimethyl sulfide (DMS), isoprene, and several monoterpenes. Computer simulations demonstrate that these reactions can dominate the atmospheric behavior of these organic compounds at night. Thus reaction with NO(3) radicals may be the unknown, nonphotochemical removal process for DMS recently invoked by Andreae and Raemdonck to explain the absence of a diurnal profile for DMS in maritime air influenced by continental air masses. Similarly, the nighttime reaction of NO(3) radicals with monoterpenes can be a dominant removal process, leading to very low monoterpene concentrations in ambient atmospheres during the early morning.

Trace nitrogenous species in urban atmospheres.

Recent results concerning the identification and measurement of nitrogenous air pollutants in the California South Coast Air Basin (CSCAB) are presented. In planning or evaluating studies of the human health effects of these pollutants, it is important to consider the entire range of species which may be present. We provide estimates of typical exposures to nitrogenous air pollutants during a single day oxidant event in the CSCAB.

Formation and fate of gaseous and particulate mutagens and carcinogens in real and simulated atmospheres.

The growing use of coal for heating and electric power generation and diesel engines in light duty motor vehicles will increase not only the existing atmospheric concentrations of criteria pollutants such as NO2, SO2, O3 and fine particulates, but also the concentrations of a number of highly reactive gaseous copollutants such as HONO, HONO2, PAN and the nitrate radical, NO3. These gaseous noncriteria pollutants are of interest not only because of their roles in the chemistry of the "clean" and polluted troposphere, including "acid rain," but also because they may pose health risks disproportionate to their relatively low ambient concentrations, and through complex heterogeneous reactions, they may serve as precursors or catalysts in the formation of "nonclassical" particulate mutagens and carcinogens such as certain nitroarenes associated with combustion generated particulate polycyclic organic matter (POM). Results of research efforts to establish current ambient levels of these noncriteria pollutants and to develop an understanding of their sources, formation and sinks are reported here. First, long pathlength (greater than or equal to 1 km) infrared and UV-visible spectroscopic studies of ambient levels of gaseous HONO, NO3, HONO2, PAN, HCHO and HCOOH in southern California atmospheres are described, and data given on their ambient concentrations. Second, an integrated chemical/microbiological investigation is described. It is directed toward identifying the nature of direct-acting mutagens found in extracts of diesel and ambient POM, as well as those formed upon exposure of environmentally relevant PAH to simulated natural and polluted atmospheres. The identification of certain of these mutagens, including a newly identified class of mutagenic PAH-lactones is discussed, along with the mechanisms of their formation and fate in the natural and polluted troposphere.