Measurements of atmospheric carboxylic acids and carbonyl compounds in São Paulo City, Brazil.

Winter atmospheric measurements of gaseous lower carbonyl and carboxylic acids were carried out simultaneously (in 1999) at two distinct urban sites located in the city of São Paulo, Brazil. The greater metropolitan area of São Paulo is the largest industrialized region of Latin America and has a highly polluted atmosphere. It has an unconventional mix of vehicle types in that a variety of gasoline blends, including oxygenated ones, are used. Mixing ratios of formic and acetic acids ranged, respectively, from 0.6 to 19.4 and from 0.1 to 10.6 ppbv in one of the sites studied and from 1.4 to 18.4 and from 0.4 to 6.7 ppbv in the other site. High values of formic to acetic ratios were found, especially in the latter site (average = 4.3), suggesting that photochemical production was the predominant source of the formic and acetic acid during the afternoon. Differing from the acids, levels of carbonyls were similar at both sites. Higher average mixing ratios of acetaldehyde and formaldehyde were found in the morning (18.9 and 17.2 ppbv) and gradually decreased from midday (9.5 and 11.8 ppbv) to evening (7.2 and 10.2 ppbv). In the morning, vehicular direct emission seemed to be the main primary source of formaldehyde and acetaldehyde, whereas at midday and evening these compounds appeared to be mainly formed by photochemistry. Secondary photochemical production of organic acids and aldehydes (rather than primary emissions from vehicles) was shown to be more important in São Paulo's atmosphere from midday to evening, particularly on days with strong solar radiation.