Ambient air measurement of acrolein and other carbonyls at the Oakland-San Francisco Bay Bridge toll plaza.

Abstract

Interest in ambient concentrations of acrolein and other alpha,beta-unsaturated aldehydes and dicarbonyls (e.g., crotonaldehyde, methyl glyoxal, glyoxal, malonaldehyde (malondialdehyde)) is growing because either they exist at high levels in motor vehicle emissions or they arise from photooxidation of other hydrocarbons emitted from mobile sources. In addition, their mutagenic, genotoxic, or carcinogenic properties are well-established, and the results of a dispersion-modeling study regarding the health risks posed by the 188 hazardous air pollutants in California attributes the highest noncancer risk to exposure to acrolein. Such modeling studies, conducted by the U.S. Environmental Protection Agency (U.S. EPA), also predict median ambient air concentrations of acrolein higher than 0.06 microg/m3, the chronic inhalation reference exposure level stipulated by the California Office of Environmental Health Hazard Assessment in counties surrounding the Oakland-San Francisco Bay Bridge. We measured acrolein and other potentially toxic carbonyls in air sampled at the San Francisco Bay Bridge toll plaza during rush hour traffic, which may be considered a "worst case scenario" for outdoor airborne carbonyls. We identified 36 carbonyls in the sample extracts, including 14 saturated aliphatic carbonyls, six unsaturated carbonyls, four aromatic carbonyls, six dicarbonyls, and six hydroxy carbonyls. Structural information to support tentative identification of carbonyls and hydroxycarbonyls was obtained by using a method that involves O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and PFBHA/bis(trimethylsilyl)trifluoroacetamide (BSTFA) derivatization in concert with gas chromatography/ion trap mass spectrometry. Most notably, we report for the first time the presence of malonaldehyde in the ambient atmospheric environment. A relatively linear relationship between retention time and the molecular weight of the derivatives was established to assist in obtaining structural information about chemicals for which authentic standards are not readily available. Levels of acrolein exceeded the California reference exposure level during morning rush hour traffic. The measured values, however, were significantly lower than estimates of county-wide average acrolein concentrations predicted by a U.S. EPA modeling study based on 1996 data. Successful regulatory efforts such as the introduction of reformulated gasoline, together with the advancement of new catalysts and fleet turnover throughout the 1990s, are likely to account for part of the gap between our determination and the 1996 levels.