Closure evaluation of size-resolved aerosol pH in the New England coastal atmosphere during summer

During summer 2002, soluble trace gases, the ionic composition of size-resolved aerosols, and meteorological conditions were measured from the National Oceanic and Atmospheric Administration ship Ronald H. Brown in coastal air along the eastern U. S. seaboard. Aerosol acidities were extrapolated from direct pH measurements in minimally diluted extracts and were also inferred from the measured phase partitioning and thermodynamic properties of HCl, HNO3, NH3, HCOOH, and CH3COOH. Median pHs for 0.75- through 25-mum geometric mean diameter (GMD) size fractions based on direct measurements (2.6-3.9) were higher than those inferred from HCl partitioning (1.7-3.3). Phase disequilibria caused negative deviations in median pHs inferred from HNO3 partitioning with aerosol size fractions greater than 2.8-mm GMD; pHs inferred for smaller size fractions (median values of 1.9-3.0) were similar to those based on HCl (median values of 1.5-3.0). The pHs inferred from NH3 partitioning were significantly lower than those estimated by other approaches; causes for this apparent bias are not known. The dominance of gas-phase HCOOH and CH3COOH was generally consistent with predicted phase partitioning with acidic aerosols. Typically large diel excursions in most gases implied corresponding variability in aerosol acidity. The pHs inferred from maximum and minimum mixing ratios of gases over each aerosol sampling interval suggested median 12-hour variations of similar to0.4-0.7 pH unit. Total acidity (H-t = H+ + undissociated acids) was greater than H+ by 1-2 orders of magnitude in all size fractions; most Ht was in the form of HSO4-.