Fluorinated compounds are environmentally persistent and have been demonstrated to bioaccumulate and contribute to climate change. The focus of this work was to better understand the atmospheric chemistry of poly- and per-fluorinated compounds in order to appreciate their impacts on the environment. Several fluorinated compounds exist for which data on climate impacts do not exist. Radiative efficiencies (REs) and atmospheric lifetimes of two new long-lived greenhouse gases (LLGHGs) were determined using smog chamber techniques: perfluoropolyethers and perfluoroalkyl amines. Through this, it was observed that RE was not directly related to the number of carbon-fluorine bonds. A structure-activity relationship was created to allow the determination of RE solely from the chemical structure of the compound. Also, a novel method was developed to detect polyfluorinated LLGHGs in the atmosphere. Using carbotrap, thermal desorption and cryogenic extraction coupled to GC-MS, atmospheric measurements can be made for a number of previously undetected compounds. A perfluoroalkyl amine was detected in the atmosphere using this technique, which is the compound with the highest RE ever detected in the atmosphere. Perfluorocarboxylic acids (PFCAs) are water soluble and non-volatile, suggesting they are not susceptible to long-range transport. A hypothesis was derived to explain the ubiquitous distribution of these compounds involving atmospheric formation of PFCAs from volatile precursors. Using smog chamber techniques with offline analysis, perfluorobutenes and fluorotelomer iodides were shown to yield PFCAs from atmospheric oxidation. Dehydrofluorination of perfluorinated alcohols (PFOHs) is poorly understood in the mechanism of PFCA atmospheric formation. Using density functional techniques, overtone-induced photolysis was shown to lead to dehydrofluorination of PFOHs. In the presence of water, this mechanism could be a sink of PFOHs in the atmosphere. Confirmation of the importance of volatile precursors was derived from examination of snow from High Arctic ice caps. This provided the first empirical evidence of atmospheric deposition. Through the analytes observed, fluxes and temporal trends, it was concluded that atmospheric oxidation of volatile precursors is an important source of PFCAs to the Arctic.

Fluorinated compounds are environmentally persistent and have been demonstrated to bioaccumulate and contribute to climate change. The focus of this work was to better understand the atmospheric chemistry of poly- and per-fluorinated compounds in order to appreciate their impacts on the environment. Several fluorinated compounds exist for which data on climate impacts do not exist. Radiative efficiencies (REs) and atmospheric lifetimes of two new long-lived greenhouse gases (LLGHGs) were determined using smog chamber techniques: perfluoropolyethers and perfluoroalkyl amines. Through this, it was observed that RE was not directly related to the number of carbon-fluorine bonds. A structure-activity relationship was created to allow the determination of RE solely from the chemical structure of the compound. Also, a novel method was developed to detect polyfluorinated LLGHGs in the atmosphere. Using carbotrap, thermal desorption and cryogenic extraction coupled to GC-MS, atmospheric measurements can be made for a number of previously undetected compounds. A perfluoroalkyl amine was detected in the atmosphere using this technique, which is the compound with the highest RE ever detected in the atmosphere. Perfluorocarboxylic acids (PFCAs) are water soluble and non-volatile, suggesting they are not susceptible to long-range transport. A hypothesis was derived to explain the ubiquitous distribution of these compounds involving atmospheric formation of PFCAs from volatile precursors. Using smog chamber techniques with offline analysis, perfluorobutenes and fluorotelomer iodides were shown to yield PFCAs from atmospheric oxidation. Dehydrofluorination of perfluorinated alcohols (PFOHs) is poorly understood in the mechanism of PFCA atmospheric formation. Using density functional techniques, overtone-induced photolysis was shown to lead to dehydrofluorination of PFOHs. In the presence of water, this mechanism could be a sink of PFOHs in the atmosphere. Confirmation of the importance of volatile precursors was derived from examination of snow from High Arctic ice caps. This provided the first empirical evidence of atmospheric deposition. Through the analytes observed, fluxes and temporal trends, it was concluded that atmospheric oxidation of volatile precursors is an important source of PFCAs to the Arctic.