Experimental determination of the partitioning of representative organic pollutants to the air-water interface.

Using glancing-angle laser-induced fluorescence (GALIF) spectroscopy as a probe, the partitioning of naphthalene, fluoranthene, pyrene, umbelliferone, phenol red, and bisphenol A from bulk solution to the air-water interface was examined in both pure water and aqueous solutions of 6 mM octanol. Previous studies provided similar Langmuir adsorption isotherms for anthracene and imidazole 2-carboxaldehyde. The surface partitioning behaviour of each compound in both environments was well described using a Langmuir adsorption model; partitioning coefficients were derived from the fits to such isotherms. Only the PAH molecules, naphthalene, fluoranthene and pyrene, saw an enhancement in the surface partitioning in octanol solution compared to pure water. The surface partitioning to pure water surfaces could be fairly well described using a one parameter linear free energy relationship based on either solubility or KOW.

Ionic Composition of Particulate Matter across Canada Shows Evidence for Near-Ubiquitous Chloride Activation and Sulfate Neutralization.

Using publicly available data from the National Air Pollution Surveillance Program, water-soluble ion mole fractions in PM2.5 and PM2.5-10 were extracted for 2010, 2012, 2013, and 2015 at six locations across Canada. Fine particle ion content was dominated by ammonium sulfate, with ammonium to sulfate ratios largely approaching 2 and no seasonal or geographic trends. Sulfate and nitrate mole fractions were negatively correlated in the fine particles, consistent with their expected pathways of entry into PM2.5. Coarse particle composition varied depending on location and season. Coastal stations were dominated by sodium and chloride year-round while inland stations showed high amounts of these ions only during the colder months, where road salt is often applied. A negative correlation between nitrate and chloride mole fractions as well as a positive correlation between nitrate concentrations and "missing" chloride provides evidence for near-ubiquitous nitrate displacement of chloride. This displacement was strongly indicated in coastal sites and also evident inland, especially during cold months. Weak evidence for nitrogen dioxide as the source of nitrate was found for inland sites, but none was found for coastal sites, suggesting a nonlocal source for the particulate nitrate precursor.