Determination of fluorinated alkyl substances in aqueous systems Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/hd76s275b

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  • Fluorinated alkyl substances, which can be persistent, toxic, and bioaccumulative, have been quantitated in many densely populated and remote regions, including in air, surface waters, groundwater, and biota; however, little is known about their transport or behavior in the environment. Wastewater effluent is one of the principal routes for introducing environmental contaminants into aquatic environments. The partitioning behavior of fluorinated alkyl substances between aqueous and particulate phases is not well characterized; thus, sorption onto sludge can be a removal mechanism of fluorinated alkyl substances from the wastewater stream. This is another route into the environment if the biosolids are land-applied. In an attempt to analyze for the fluorinated alkyl substances in wastewater, known aqueous-film-forming-foam (AFFF)-laden groundwater sampled from 3 military bases was used to develop an assay using liquid chromatography (LC), electrospray ionization (ESI) tandem mass spectrometry (MS/MS). While working on the method development, fluorotelomer sulfonates were detected at Wurtsmith AFB, MI, and Tyndall AFB, FL, where total fluoroatkyl sulfonates ranged respectively from below quantitation (≤0.60 μg/L) to 182 μg/L and from 1100 μg/L to 14,600 μg/L. The LC ESI-MS/MS method was modified to quantitate fluorinated alkyl sulfonates in wastewater by incorporating a htgh volume sample loop (500 μL), which lowered detection and quantitation limits by at least a factor of 50. This method was applied to 24 h composites of influents and effluents collected from treatment plants distributed nationwide. Fluorinated alkyl substances were observed at all 10 plants sampled, and each wastewater treatment plant was found to have a unique distribution of fluorinated alkyl substances, despite similar treatment processes. In 9 out of the 10 plants sampled, at least one class of fluorinated alkyl substance exhibited significant increases in the effluent as compared to the influent levels. The high-volume-injection LC ESI-MS/MS method was also used to monitor the mass flows of perfluoroalkyl sulfonates and carboxylates through a municipal wastewater treatment plant for 10 d. The perfluoroalkyl carboxylates were overall removed by the wastewater treatment process (25-40% removal). Perfluoroalkyl sulfonates were found to increase significantly (~200%) in the final effluent, and the fluoroalkyl sulfonamide acetic acids were found to increase by approximately 500% throughout the sludge process. From this plant, significant quantities of fluorochemicals are discharged with treated wastewater and biosolids, indicating that wastewater treatment plants are point sources of fluorinated alkyl substances and must be considered when determining origins and behavior of fluorinated alkyl substances in the environment.
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