Grantee Research Project Results
2003 Progress Report: Occurrence and Behavior of Perfluorinated Surfactants in Municipal Wastewater Treatment Systems
EPA Grant Number: R829025Title: Occurrence and Behavior of Perfluorinated Surfactants in Municipal Wastewater Treatment Systems
Investigators: Field, Jennifer , Barofsky, Douglas
Institution: Oregon State University
EPA Project Officer: Packard, Benjamin H
Project Period: September 1, 2001 through August 31, 2004
Project Period Covered by this Report: September 1, 2002 through August 31, 2003
Project Amount: $342,764
RFA: Exploratory Research to Anticipate Future Environmental Issues (2000) RFA Text | Recipients Lists
Research Category: Water , Aquatic Ecosystems , Ecological Indicators/Assessment/Restoration
Objective:
The overall goal of this research project is to determine the occurrence and distribution of perfluorinated surfactants in municipal wastewaters and in surface waters receiving municipal wastewater effluents. The specific objectives of this research project are to: (1) develop quantitative methods for the determination of perfluoroalkyl sulfonates and carboxylates, telomer sulfonates, and sulfonamide-based chemicals in municipal wastewaters and sludges; and (2) determine the mass flows of these fluorinated chemicals during municipal wastewater plant treatment.
Progress Summary:
A direct-injection, liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed to quantify a suite of fluorotelomer sulfonate surfactants in groundwater collected from military bases where fire-training activities occurred. The 4:2, 6:2, and 8:2 fluorotelomer sulfonates were detected and quantified in groundwater from two of the three military bases. The total fluorotelomer sulfonate concentrations observed at Wurtsmith Air Force Base (AFB), MI , and Tyndall AFB, FL, ranged respectively from below quantitation (≤ 0.60 µg/L) to 182 µg/L and from 1,100 µg/L to 14,600 µg/L. Analyses of a fluorotelomer-based aqueous film forming foam (AFFF) concentrate by negative ion fast atom bombardment/mass spectrometry and LC/MS/MS analyses indicate that the principal anionic fluorosurfactants in a telomer-based AFFF product are fluoroalkylthioamido sulfonates, and that fluorotelomer sulfonates are less than 1 percent of the mixture.
High-volume (e.g., 200-500 mL), direct-injection analysis for LC/MS/MS was developed as a means for concentrating fluorochemical analytes in municipal wastewater, which improves sensitivity and eliminates the need for sample concentration steps such as solid phase extraction. With this approach, perfluorosulfonates and perfluorocarboxylates as well as telomer sulfonates were determined in municipal wastewater influents and effluents.
For the analysis of sulfonamides and their alcohol derivatives, gas chromatography/tandem mass spectrometry (GC/MS/MS) was compared to LC/MS/MS. Under electrospray ionization-LC/MS/MS, sulfonamide alcohols only produced unstable acetate-adduct precursor ions, and these precursor ions gave only acetate as the product ion, which lacks structural specificity. On the other hand, GC/MS/MS with chemical ionization produced structurally significant product ions. For this reason, GC/MS/MS was selected for further use in methods development. The conditions necessary to ensure quantitative and reproducible analysis by GC/MS/MS were determined, and steps were taken to develop a solid-phase extraction method for sulfonamides and their alcohols in municipal wastewater.
Significance
We have made the first identification of telomer sulfonates in groundwater and perhaps the first identification in any aqueous environmental samples. Furthermore, we have unequivocally established that the 6:2 telomer sulfonate should not be used as a surrogate or internal standard for environmental analysis. We have determined that although it would be desirable to combine the analyses for all fluorochemicals of interest into a single LC/MS/MS method, it is not realistic. This confirms that GC/MS/MS is the method of choice given the availability of instrumentation at the current time.
Relationship to Goal of Award
Year 2 results directly correspond to the objective to create sensitive and selective analytical methods for the detection of fluorosurfactants in aqueous wastewater matrices. These analytical methods will allow us to meet the overall objective of the project, which is to determine the mass flow of fluorochemicals through municipal wastewater treatment plants.
Relevance and Practical Application
The methodology developed in Year 2 of the project can be applied directly to the analysis of groundwater contaminated with three classes of fluorochemicals. The high-volume, direct-injection approach can be applied to the analysis of municipal wastewaters.
Future Activities:
We will continue to optimize: (1) the high-volume injection LC/MS/MS method for the analysis of perfluorosulfonates, carboxylates, and telomer sulfonates in wastewater; and (2) the solid-phase extraction GC/MS/MS method for sulfonamide and sulfonamide derivative analysis in wastewater and sludges. We are collaborating with Dr. Luthy at Stanford University on the analysis of municipal sludges for perfluorosulfonates, carboxylates, and telomer sulfonates.
Journal Articles on this Report : 2 Displayed | Download in RIS Format
Other project views: | All 12 publications | 3 publications in selected types | All 3 journal articles |
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Field JA, Schultz M, Barofsky D. Identifying hydrocarbon and fluorocarbon surfactants in specialty chemical formulations of environmental interest by fast atom bombardment/mass spectrometry. Chimia International Journal for Chemistry 2003;57(9):556-560. |
R829025 (2003) |
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Schultz MM, Barofsky DF, Field JA. Fluorinated alkyl surfactants. Environmental Engineering Science 2003;20(5):487-501. |
R829025 (2002) R829025 (2003) |
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Supplemental Keywords:
fluorochemicals, fluorosurfactants, liquid chromatography, mass spectrometry, groundwater, wastewater, sludge, perfluoroalkylsulfonates, perfluoroalkylcarboxylates, fluorotelomer sulfonates, perfluoroalkylsulfonamides,, Scientific Discipline, Water, TREATMENT/CONTROL, Wastewater, Environmental Chemistry, Environmental Engineering, Water Pollution Control, real time analysis, wastewater treatment, perfluorinated surfactants, municiple wastewater sludge, wastewater remediation, sludge treatment, chemical contaminants, municipal wastewater treatment, liquid chromatography / mass spectrometry, aqueous waste streamProgress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.