Influence of biomass combustion emissions on the distribution of acidic trace gases over the southern Pacific basin during austral springtime

This paper describes the large‐scale distributions of HNO 3 , HCOOH, and CH 3 COOH over the central and South Pacific basins during the Pacific Exploratory Mission‐Tropics (PEM‐Tropics) in austral springtime. Because of the remoteness of this region from continental areas, low part per trillion by volume (pptv) mixing ratios of acidic gases were anticipated to be pervasive over the South Pacific basin. However, at altitudes of 2–12 km over the South Pacific, air parcels were encountered frequently with significantly enhanced mixing ratios (up to 1200 pptv) of acidic gases. Most of these air parcels were centered in the 3–7 km altitude range and occurred within the 15°−65°S latitudinal band. The acidic gases exhibited an overall general correlation with CH 3 Cl, PAN, and O 3 , suggestive of photochemical and biomass burning sources. There was no correlation or trend of acidic gases with common industrial tracer compounds (e.g., C 2 Cl 4 or CH 3 CCl 3 ). The combustion emissions sampled over the South Pacific basin were relatively aged exhibiting C 2 H 2 /CO ratios in the range of 0.2–2.2 pptv/ppbv. The relationships between acidic gases and this ratio were similar to what was observed in aged air parcels (i.e., >3–5 days since they were over a continental area) over the western North Pacific during the Pacific Exploratory Mission‐West Phases A and B (PEM‐West A and B). In the South Pacific marine boundary layer a median C 2 H 2 /CO ratio of 0.6 suggested that this region was generally not influenced by direct inputs of biomass combustion emissions. Here we observed the lowest mixing ratios of acidic gases, with median values of 14 pptv for HNO 3 , 19 pptv for HCOOH, and 18 pptv for CH 3 COOH. These values were coincident with low mixing ratios of NO x (<10 pptv), CO (≈50 parts per billion by volume (ppbv)), O 3 (< 20 ppbv), and long‐lived hydrocarbons (e.g., C 2 H 6 <300 pptv). Overall, the PEM‐Tropics data suggest an important influence of aged biomass combustion emissions on the distributions of acidic gases over the South Pacific basin in austral springtime.