Perfluoroalkyl carboxylates (PFCAs) and perfluoroalkane sulfonates (PFSAs)are anthropogenic fluorinated surfactants that have been detected in almost every environmental compartment studied, yet their production and applications are far outweighed by those of other higher molecular weight fluorinated surfactants used in commerce. These fluorinated surfactants are widely incorporated in commercial products, yet their post-application fate has not been extensively studied. This thesis examines various biological and environmental processes involved in the fate of these surfactants upon consumer disposal. Specific focus was directed towards the environmental chemistry of polyfluoroalkyl phosphate esters (PAPs), perfluoroalkyl phosphonates (PFPAs), and perfluoroalkyl phosphinates (PFPiAs), and their potential roles as sources of perfluoroalkyl acids (PFAAs) in the environment. PAPs are established biological precursors of PFCAs, while PFPAs and PFPiAs are newly discovered PFAAs in the environment. Incubation with wastewater treatment plant (WWTP) microbes demonstrated the ability of PAPs to yield both fluorotelomer alcohols (FTOHs), which are established precursors of PFCAs, and the corresponding PFCAs themselves. WWTP biosolids-applied soil-plant microcosms revealed that PAPs can significantly accumulate in plants along with their degradation metabolites. This has implications for potential wildlife and human exposure through the consumption of plants grown and/or livestock raised on farmlands that have been amended with contaminated biosolids. A number of compound-and environmental-specific factors were observed to significantly influence the partitioning of PFPAs and PFPiAs between aqueous media and soil, as well as, aquatic biota during sorption and bioaccumulation experiments respectively. In both processes, PFPAs were primarily observed in the aqueous phase, while PFPiAs predominated in soil and biological tissues, consistent with the few environmental observations of these chemicals made to date. Detection of the PAP diesters (diPAPs), PFPiAs, and fluorotelomer sulfonates (FTSAs),all of which are used commercially, in human sera is evidence of human exposure to commercial fluorinated products, but the pathways by which this exposure occurs remain widely debated. Overall, this work presents novel findings on the environmental fate of commercial fluorinated surfactants and each of the process studied shows a clear link between the use of commercial products and the fluorochemical burden currently observed in the environment.

Perfluoroalkyl carboxylates (PFCAs) and perfluoroalkane sulfonates (PFSAs)are anthropogenic fluorinated surfactants that have been detected in almost every environmental compartment studied, yet their production and applications are far outweighed by those of other higher molecular weight fluorinated surfactants used in commerce. These fluorinated surfactants are widely incorporated in commercial products, yet their post-application fate has not been extensively studied. This thesis examines various biological and environmental processes involved in the fate of these surfactants upon consumer disposal. Specific focus was directed towards the environmental chemistry of polyfluoroalkyl phosphate esters (PAPs), perfluoroalkyl phosphonates (PFPAs), and perfluoroalkyl phosphinates (PFPiAs), and their potential roles as sources of perfluoroalkyl acids (PFAAs) in the environment. PAPs are established biological precursors of PFCAs, while PFPAs and PFPiAs are newly discovered PFAAs in the environment. Incubation with wastewater treatment plant (WWTP) microbes demonstrated the ability of PAPs to yield both fluorotelomer alcohols (FTOHs), which are established precursors of PFCAs, and the corresponding PFCAs themselves. WWTP biosolids-applied soil-plant microcosms revealed that PAPs can significantly accumulate in plants along with their degradation metabolites. This has implications for potential wildlife and human exposure through the consumption of plants grown and/or livestock raised on farmlands that have been amended with contaminated biosolids. A number of compound-and environmental-specific factors were observed to significantly influence the partitioning of PFPAs and PFPiAs between aqueous media and soil, as well as, aquatic biota during sorption and bioaccumulation experiments respectively. In both processes, PFPAs were primarily observed in the aqueous phase, while PFPiAs predominated in soil and biological tissues, consistent with the few environmental observations of these chemicals made to date. Detection of the PAP diesters (diPAPs), PFPiAs, and fluorotelomer sulfonates (FTSAs),all of which are used commercially, in human sera is evidence of human exposure to commercial fluorinated products, but the pathways by which this exposure occurs remain widely debated. Overall, this work presents novel findings on the environmental fate of commercial fluorinated surfactants and each of the process studied shows a clear link between the use of commercial products and the fluorochemical burden currently observed in the environment.