Characterization of the size-segregated water-soluble inorganic ions at eight Canadian rural sites

Abstract. Size-segregated water-soluble inorganic ions, including particulate sulphate (SO₄^2-), nitrate (NO₃^-), ammonium (NH₄⁺), chloride (Cl^-), and base cations (K⁺, Na⁺, Mg²⁺, Ca²⁺), were measured using a Micro-Orifice Uniform Deposit Impactor (MOUDI) during fourteen short-term field campaigns at eight locations in both polluted and remote regions of eastern and central Canada. The size distributions of SO₄^2- and NH₄⁺ were unimodal, peaking at 0.3–0.6 µm in diameter, during most of the campaigns, although a bimodal distribution was found during one campaign and a trimodal distribution was found during another campaign made at a coastal site. SO₄^2- peaked at slightly larger sizes in the cold seasons (0.5–0.6 µm) compared to the hot seasons (0.3–0.4 µm) due to the higher relative humidity in the cold seasons. The size distributions of NO₃^- were unimodal, peaking at 4.0–7.0 µm during the warm-season campaigns, and bimodal, with one peak at 0.3–0.6 µm and another at 4–7 µm during the cold-season campaigns. A unimodal size distribution, peaking at 4–6 µm, was found for Cl^-, Na⁺, Mg²⁺, and Ca²⁺ during approximately half of the campaigns and a bimodal distribution, with one peak at 2 µm and the other at 6 µm, was found during the rest of the campaigns. For K⁺, a bimodal distribution, with one peak at 0.3 µm and the other at 4 µm, was observed during most of the campaigns. Seasonal contrasts in the size-distribution profiles suggest that emission sources and air mass origins were the major factors controlling the size distributions of the primary aerosols while meteorological conditions were more important for the secondary aerosols.

The dependence of the particle acidity on the particle size from the nucleation mode to the accumulation mode was not consistent from site to site or from season to season. Particles in the accumulation mode were more acidic than those in the nucleation mode when submicron particles were in the state of strong acidity; however, when submicron particles were neutral or weakly acidic, particles in the nucleation mode could sometimes be more acidic. The inconsistency of the dependence of the particle acidity on the particle size should have been caused by the different emission sources of all the related species and the different meteorological conditions during the different campaigns. The results presented here at least partially explain the controversial phenomenon found in previous studies on this topic.