Inorganic chlorine and bromine in coastal New England air during summer



[1] During summer 2004, a comprehensive suite of reactive trace gases (including halogen radicals and precursors, ozone, reactive N, soluble acids, and hydrocarbons), the chemical and physical characteristics of size-resolved aerosols, actinic flux, and related physical conditions were measured at Appledore Island, Maine, as part of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). Sea-salt mass averaged 4 to 8 times lower than that over the open North Atlantic Ocean. Production in association with sea salt was the primary source for inorganic Cl and Br. Acid displacement of sea-salt Cl primarily by HNO3 sustained high HCl mixing ratios (often >2000 pptv) during daytime. Median pHs for the larger sea-salt size fractions (geometric mean diameters, GMDs ≥ 2.9 μm) ranged from 3.1 to 3.4; median pHs for sub-μm size fractions were ≤ 1.6. Cl* (including HOCl and Cl2) ranged from <20 to 421 pptv Cl but was less than the detection limit (DL) during most sampling intervals. Periods during which Cl* was consistently detectable corresponded to relatively clean conditions, multiday transport over water, and relatively low actinic flux. At high HCl mixing ratios (>1000 pptv), HCl + OH sustained steady state Cl-atom concentrations in the range of 104 cm−3. When detectable, photolysis of Cl* was generally the dominant source of atomic Cl; steady state concentrations of Cl atoms were frequently in the range of 104 to 105 cm−3. At these concentrations, Cl played an important role in the chemical evolution of polluted coastal air. Br radical chemistry was relatively unimportant.