Formic acid and acetic acid: Emissions,atmospheric formation and dry deposition at two southern California locations

Emission rates, in situ formation rates and removal rates by dry deposition are estimated for formic acid (HCOOH, C1) and acetic acid (CH₃COOH, C2), which are the most abundant acids in southern California air and together account for much of the airborne acidity and are the leading contributors to acid dry deposition. Using data for eight unreactive tracers, direct emission rates during the fall 1987 are estimated to be 5.6 and 12.8 metric tons d⁻¹ for C1 and C2, respectively, at a coastal source-dominated site. These emissions rates increase to 9.6(C1) and 20.4(C2) metric tons d⁻¹ during the summer. In situ formation in the atmosphere via the ozone-olefin reaction is an important source for both acids. This reaction produces an estimated 25.0 and 10.1 metric tons d⁻¹ of C1 and C2, respectively, during the day and 34.5 (C1) and 4.3 (C2) metric tons d⁻¹ at night. More acetic acid than formic acid is emitted by direct sources, with C2/C1 emission rate ratios of 2.1–2.3. The reverse is true of in situ formation, with C1/C2 production rate ratios of 2.5 (day) and 8.0 (night). Dry deposition removal rates depend on season (fall > summer) and location (inland > coastal) and are 22–52 metric tons d⁻¹ for C1, and 32–83 metric tons d⁻¹ for C2. Source (emissions + in situ formation) and sink (dry deposition) terms are of the same magnitude in all six cases studied and balance each other well in three of these cases. Uncertainties in emission, in situ production and removal rates are discussed and reflect uncertaintes in olefin and unreactive tracer emission rates, yields of organic acids from the Criegee biradical (ozone-olefin reaction), and dry deposition velocity, respectively.