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(086) A kinetic study of the OH radical-initiated oxidation of partially fluorinated alcohols.
Ellis, David*,1, Martin, Jonathan1, Lane, Doug2, Muir, Derek3, Mabury, Scott1, 1 University of Toronto, Toronto, Ontario, Canada2 Environment Canada, Toronto, Ontario, Canada3 National Water Research Institute, Environment Canada, Burlington, Ontario, Canada
ABSTRACT- A kinetic and product study involving the oxidation of fluorinated alcohols, e.g. sulfonamide derivatives of perfluorooctane sulphonate (PFOS) and fluorotelomer alcohols, through their reaction with hydroxyl radicals (OH) was conducted. Reactions were carried out in a 10, 000 L smog chamber with OH being produced through the photolysis of iso-propylnitrite. Using cyclohexane as a reference compound, which has a well established second order rate constant rate, the kinetics of the reaction with OH for the alcohols were determined using the relative rate method. Real time data for the loss of the parent molecule was collected by direct analysis using solid phase micro extraction (SPME) followed by GC-MS analysis. Results estimate the second order rate constant for 1H, 1H, 2H, 2H perfluorooctan-1-ol to be 4.79 x 10-12 cm3 molecule-1 s-1. Products were extracted as a function of time and collected using XAD, carbonate based denuders, aqueous bubblers and condensation of gaseous samples at low temperature (-78C) into organic solvents. Product identification and quantitation was carried out using a suite of analytical techniques including GC/MS, LC/MS/MS, and 19F NMR.
Key words: Fluoroalcohol, Telomer, Atmospheric Fate, Degradation
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