Environ. Sci. Technol. 2006, 40, 1447-1453

tions also generates these persistent environmental con- Significant Residual Fluorinated taminants (6, 7). Perfluorinated acids such as PFOA have Present in Various been a concern to environmental scientists and regulators in recent years due to their ubiquity in various environmental Fluorinated Materials matrices, particularly in blood samples of occupationally exposed workers but most specially the general human population (8). Its carcinogenic effects (9) and developmental MARY JOYCE A. DINGLASAN-PANLILIO toxicity to rats (10) have also instigated the demand for further AND SCOTT A. MABURY* study of these compounds and their sources by regulators Department of Chemistry, University of Toronto, 80 Saint to determine potential risk, if any, to humans. It has been George Street, Toronto, Ontario M5S 3H6 Canada shown that metabolism of the 8:2 telomer in rats produces PFOA (11, 12) which has further emphasized that PFOA and other PFCAs found in human blood may be partially due to exposure to these volatile compounds (12). Polyfluorinated telomer alcohols and sulfonamides are In addition, isomeric profiles of PFCAs detected in polar bears classes of compounds recently identified as precursor suggest they originated primarily from a linear isomer source molecules to the perfluorinated acids detected in the (13). environment. Despite the detection and quantification of Similarly, the perfluoroalkyl sulfonamido alcohols have these volatile compounds in the atmosphere, their sources been suggested to be precursors of perfluoroalkane sul- remain unknown. Both classes of compounds are used fonates, another class of perfluorinated acids (2); they have in the synthesis of various fluorosurfactants and incorporated also been detected at appreciable amounts in both outdoor in polymeric materials used extensively in the carpet, (1, 2) and indoor air (14). Biotransformation studies of N-ethyl textile, and paper industries. This study has identified the perfluorooctane sulfonamidoethanol (NEtFOSE) have con- presence of residual unbound fluoro telomer alcohols firmed the production of perfluorooctane sulfonate (PFOS) (FTOHs) in varying chain lengths (C6-C14) in several as a terminal metabolite in rats (15). PFOS like PFOA, has been detected in various environmental matrices and found commercially available and industrially applied polymeric resistant to degradation (16). Research in our laboratory is and surfactant materials. NMeFOSE, a perfluoroalkyl currently investigating whether sulfonamido alcohols un- sulfonamido alcohol, was also detected in a commercially dergo atmospheric degradation to produce PFOS. In response available carpet protector product. A method was to the widespread detection of PFOS in the environment, developed to remove these residual compounds from 3M, a major manufacturer of perfluorinated sulfonamides polymeric and surfactant materials by dispersion in water voluntarily phased out their production of compounds with and stripping of the volatiles using a constant flow of perfluorooctane chemistry in 2000-2002. These compounds air and trapping on XAD resin. Using gas chromatography include the sulfonamido alcohols, N-methyl (NMeFOSE) as mass spectrometry analysis, it was determined that the well as N-ethyl (NEtFOSE) perfluorooctane sulfonamidoet- fluorinated materials examined consist of 0.04-3.8% residual hanol. alcohols on a fluoro alcohol to dry mass basis. These The sources of both and sulfonamido alcohols have yet to be clearly identified since they are not values indicate that residual alcohols, left unreacted and understood to be directly used in industrial or commercial unbound from the manufacturing process of fluorinated applications. They are, however, largely used in the synthesis polymers and surfactants, could be a significant source of of various fluorosurfactants as well as incorporated into a the polyfluorinated telomer alcohols and sulfonamides wide array of fluorinated polymers. released into the environment. This study suggests that Fluorinated polymers and surfactants have been in use elimination or reduction of these residual alcohols from all for over half a century and have been incorporated into a marketed fluorinated polymers and fluorosurfactants is vast array of products. These polymers are used widely in key in reducing the prevalence of perfluorinated acids formed various industries such as paints, carpet, and paper coatings in the environment. (17) and recently have found their way into other commercial products such as household cleaning agents (18). The widespread application of these polymers can be directly linked to their unique ability as effective surface-active agents, Introduction delivering both water and stain repellency. Fluorotelomer Compounding evidence has been reported recently that based polymers are characterized by a back- supports the hypothesis that fluorinated telomer alcohols bone, from which telomer alcohols (FTOHs) of various chain (FTOHs) can act as precursors to the perfluorinated acids lengths (C6-18, or 4:2 up to 16:2 FTOHs) are appended (PFCAs) that have been detected widely in the environment. through ester, amide, urethane, and ether linkages (19). FTOHs were found pervasive (11-165 pg m-3) in the North Polymers make up approximately 80% of the reported American atmosphere (1, 2) and have been identified as a production in the fluorotelomer market (20). A critical source of a suite of perfluorinated acids through atmospheric question is whether the alcohols observed in the atmosphere degradation (3). Extensive kinetic and mechanistic studies are a consequence of the scission at the polymer linkage of the FTOHs with Cl atoms and OH radicals have demon- releasing the fluoro alcohols, or merely caused by sufficient strated the formation of PFCAs as degradation products (4, residual material escaping directly from the fluorinated 5). It has been determined, in a number of experiments, that polymer or surfactants. biotic degradation of telomer alcohols under aerobic condi- This investigation has specifically sought to quantify unbound FTOHs as well as the sulfonamido alcohols, * Corresponding author phone: (416) 978-1780; e-mail: smabury@ hereafter referred to as “residuals”, from various fluorinated chem.utoronto.ca. materials, prior to or following application to consumer or

10.1021/es051619+ CCC: $33.50  2006 American Chemical Society VOL. 40, NO. 5, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1447 Published on Web 01/25/2006 FIGURE 1. Stylized schematic of postulated steps leading to the production of telomer-based polymers using 8:2 FTOH as an example. The potential source of unreacted telomer alcohols is depicted from the reaction producing the monomer and leading to its point of release to the environment from polymeric materials if left unpurified. Polymeric materials produced will have a mixture of varying chain lengths of perfluorinated and hydrocarbon chains as well as varying carbon backbone depending on reactants used. industrial products to assess the potential contribution to loss of volatiles. Materials that caused excessive foaming such the flux of these compounds to the environment. These as Zonyl FSO-100 and Zonyl FSE, were put on a shaker at 140 residual alcohols, presumably a function of incomplete rpm for continuous mixing. The vessels were tightly sealed synthesis or lack of purification prior to marketing of materials and carbon filtered in-house air was sparged through the (Figure 1), may be a significant source of release to the vessels at a flow rate of ∼40 mL min-1. Vessels were stored environment. Quantification and identification of residuals at room temperature. A schematic of the experimental setup from seven different commercially and industrially available can be found in the Supporting Information. Each compound fluorinated materials were performed using a purge and trap was analyzed, generally in triplicate or N ) 6, and a blank method coupled with gas chromatography-mass spectrom- vessel was included for each batch of experiments. Blank etry analysis. Commercially available materials are those vessels consisted of deionized water without addition of any that are available to retail consumers, whereas industrially fluorinated material and were treated the same as the spiked applied materials are those that are not generally available vessels. Vessels were purged continuously for duration of up to regular retail consumers but instead are recommended to 3 weeks with intermittent sampling of the XAD cartridges. for the use of manufacturers and industry. All fluorinated The XAD resin and the glass wool from the cartridges were materials studied may or may not contain other nonfluori- extracted using two 5 mL aliquots of ethyl acetate and both nated components in their formulation. This study identifies fractions were subsequently combined. Samples of 2 mL a source of these precursor compounds, which may ultimately each were then transferred to autosampler vials for gas comprise a significant fraction of the contribution to the chromatographic analysis. Scotchgard spiked samples were perfluorinated acids in the environment. blown down to a final volume of 200 µL using a gentle stream of purified nitrogen prior to analysis due to higher detection Materials and Methods limits for NMeFOSE but were otherwise prepared analogous Chemicals and Standards. Zonyl FSO-100 and Zonyl FSE to the other materials studied. New cartridges were installed were obtained from DuPont chemicals (Wilmington, DE). in the vessels after each sampling period. Teflon Advance Carpet Protector was purchased from Kleen Instrumental Analysis and Quantification. Sample analy- Kuip Supply Mart Inc. (Toronto, ON) and polyfox-L-diol was ses were carried out using a Hewlett-Packard 6890 gas provided by Omnova Solutions Inc. (Fairlawn, OH). Moto- chromatograph equipped with a 5973 inert mass spectrom- master windshield fluid with Teflon was purchased from eter detector. Optimal separation of the FTOHs and NMe- Canadian Tire (Toronto, ON); Scotchgard Rug and Carpet FOSE was done using a 30 m Rtx-35MS with Intra Guard Protector was purchased from Home Depot (Toronto, ON) column (0.25 mm i.d., 0.5 µm film thickness, Chromato- and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl graphic Specialties, Brockville, ON). The following GC oven methacrylate (97%) was purchased from Aldrich (Oakville, program was employed: initial temperature of 45 °C held ON). Fluorotelomer alcohols (FTOHs) 4:2, 6:2, 8:2, and 10:2 for 2 min; 10 °C min-1 ramp to 95 °C; 30 °C min-1 ramp to standards (all 97%) were purchased from Oakwood Products, 150 °C min-1;7°C min-1 ramp to 180 °C; and a final ramp Inc. (West Columbia, SC) and 3M Corp. (St. Paul, MN) of 50 °C min-1 to 240 °C and held for 2 min. Helium was used generously provided the standard for N-methyl perfluo- as the carrier gas at a flow rate of 1 mL min-1 with pulsed rooctane sulfonamidoethanol (NMeFOSE). splitless injection at an initial pressure of 20 psi at 220 °C for Preparation of Experimental Vessels. Purge and trap 1.2 min followed by an injector purge at 40.0 mL min-1 for vessels were made using 1 L media bottles (Pyrex) with caps 0.8 min. Definitive identification of fluoro alcohols was drilled to accommodate Orbo Amberlite XAD-2 cartridges performed under both electron ionization (EI) and positive (100 mg) (Supelco, Bellefonte, PA) and gas diffuser tubes chemical ionization (PCI) modes. Quantification proceeded (Pyrex, VWR International Ltd., Mississauga, ON). Distilled under PCI in single ion monitoring mode, and the molecular deionized water (500-750 mL) was added to the vessels along ion (M + 1) was monitored for all target analytes (4:2, 6:2, with 10-100 mg of the fluorinated materials of interest. These 8:2, 10:2, 12:2, and NMEFOSE). Calibration was performed aqueous suspensions were manually shaken thoroughly and using external standards prepared in ethyl acetate and ranging extra care was taken to ensure that the transfer of fluorinated in concentration from 25 to 500 pg µL-1 for the telomer materials to the vessels was done quickly to ensure minimal alcohols and 2.5 to 500 ng µL-1 for the NMeFOSE. Standards

1448 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 5, 2006 were run between each sample set (i.e., 4-6 samples) and respect to their basic chemistry or to the presence of fluoro- the mean response was used to plot a calibration curve. Good chemical residuals (21). Teflon Advance Carpet Protector is linearity was observed with typical r2 > 0.98 and retention a mixture containing both urethane and acrylic FTOH based times for all analytes of interest were well conserved (( 0.04 copolymers (22). Scotchgard Rug and Carpet protector is min). Limit of quantitation was defined as the lowest standard reported to contain a mixture of fluoroalkyl copolymers as to give a signal-to-noise ratio g10, corresponding to 25 and well as other acrylic based polymers (23). Fluorotelomer based 2.5 ng µL-1 for the telomer alcohols and NMeFOSE, respec- surfactants such as Zonyl FSO-100 and Zonyl FSE were also tively. studied. These compounds are industrial scale products Dry Mass Determination. To normalize the residual fluoro obtained directly from the producer and not generally alcohols measured from the various fluorinated polymers available to regular retail consumers. FSO-100 is described and surfactants, values presented in this investigation are as an ethoxylated nonionic fluorosurfactant able to impart expressed as mass of fluoro alcohols to dry mass of material low aqueous surface tensions at low concentrations. It has examined. Dry masses were obtained by measuring the mass a generic formula Rf-CH2CH2O(CH2CH2)xH where Rf )F(CF2- of an aliquot of the polymer or surfactant before and after CF2)y; x can be 0 to ∼15 and y ) 1to∼7. Its recommended storage in a desiccator at room temperature for several days. applications include incorporation into caulks, paints, coat- It is assumed that the fluorinated polymeric or surfactant ings, and adhesives (24). Zonyl FSE is a water-soluble, anionic material was not volatile and was not lost during the drying phosphate fluorosurfactant recommended for use in floor process. Some of the fluorinated materials examined con- waxes and coatings. Its structure consists of (RfCH2CH2O)xP- tained other compounds in their formulations such as (O)(ONH4)y where x and y ) 1 or 2 and again the Rf- is a glycol along with varying amounts of water. perfluorinated chain containing 1-7 carbons (25). The Expressing the quantity of fluoro alcohols in this fashion was synthesis of fluorotelomer based polymeric compounds is deemed as the most appropriate method for direct com- also known to proceed via the polymerization of telomer- parison between different materials. This expression should based monomers (Figure 1), hence a monomer 3,3,4,4,5,5,6,6, provide a conservative estimate of the amounts of residuals 7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (8:2 measured and a value that allows comparison across methacrylate) was also investigated to compare the amounts materials and further studies. It is an attempt to prevent of residuals obtained from this unpolymerized compound confusion in the reporting of residual amounts. It would be to those of polymeric and surfactant type materials. Polyfox- preferable to report percent residual FTOHs, for example L-diol, a fluorinated polyoxetane that is not commercially based on total FTOHs on the polymer, but this requires data available nor industrially applied, was also a subject of this that to date are not generally available. study. Polyfluorooxetanes are synthesized using the polym- Quality Control and Assurance. Spike and recovery erization of fluorinated oxetane monomers (26). This product experiments were performed to validate the applicability of is an example of a well-characterized polymeric material the purge and trap vessels. Fluorinated material was spiked obtained directly from industry containing an ether-based into the vessels and stripped of residuals. Known amounts polymer linkage. Finally, a windshield washer fluid available of telomer alcohols and NMeFOSE were then added to the at common hardware and retail stores in Ontario, Canada same vessels, purged, trapped, and quantified. Recovery of called Motomaster Windshield Washer with Teflon was also target analytes was >80% ( 20 for all compounds except the examined to determine whether new products that have 4:2 FTOH where recoveries were <50%. Breakthrough recently incorporated fluorinated polymers in their formula- portions of the XAD cartridges were analyzed separately to tion would also be sources of volatile fluorinated alcohols. ensure breakthrough of analyte did not compromise the Unbound fluorinated alcohols were detected in all seven analysis. The 4:2 FTOH was readily found in these break- materials analyzed in this study. Scotchgard carpet and rug through analyses, which suggests poor recoveries were due protector, the only nontelomer based material analyzed, had to inefficient trapping. Values expressed were not corrected free NMeFOSE detected using the purge and trap method. for recovery values. It is important to note that this product was of the initial formulation prior to the withdrawal of perfluoroctane sulfonyl Results and Discussion fluoride (POSF) based materials and other related sulfona- Recent investigations into the environmental fate of FTOHs mides in 2000-2002 by 3M and is no longer produced. The and perfluorinated sulfonamides have provided further detection of NMeFOSE as residuals clearly reflects the evidence that they undergo degradation to pervasive and presence of perfluorooctyl-based compounds. All other recalcitrant perfluorinated acids. In earlier studies, we have materials consisted of free FTOHs of varying chain length. suggested that fluorinated polymers and fluorosurfactants, Purging of the Teflon Advance product resulted in known to incorporate these volatile compounds, may be a detection of unbound telomer alcohols with chain lengths source of these alcohols through fugitive emission of residuals ranging from 8 to 14 carbons (6:2 up to 12:2 FTOHs). The 8:2 or as they degrade post-application (2, 6). In this study, seven fluorotelomer alcohol (8:2 FTOH) was found in greatest different fluorinated materials, ranging from industrially abundance, followed by the 10:2 then the 6:2. The 12:2 FTOH applied to direct consumer products, were all found to consist was also identified in an earlier range finding study using of free or unbound fluorinated alcohols. These compounds solid phase microextraction (SPME) headspace analysis but were quantified to determine their overall contribution to was below the limit of quantitation when purge and trap the accumulation of fluoro alcohols in the atmosphere and analysis was utilized. The lack of authentic 12:2 FTOH ultimately of PFCAs to the environment. standard prevented spike and recovery analysis and the low The materials analyzed included two commercially avail- levels measured by purge and trap analysis could have been able products known as Teflon Advance Carpet Protector due to poor recovery of this compound. A typical GCMS and Scotchgard Rug and Carpet Protector. These products chromatogram is shown in Figure 2. The identities of the are marketed as a post-application treatment for carpets to telomer alcohols were confirmed using both their EI and PCI infer water and soil repellency and are readily available at spectra (inset). Analysis applying positive chemical ionization hardware and carpet care retail stores. These products are gave a strong signal for the molecular ions m/z 365, 465, and relevant in the study because of their similarity to industrial 565 for 6:2, 8:2, and 10:2, respectively, where each telomer scale products. Fluorinated polymers and surfactants for- alcohol differs by 100 molecular mass units. The characteristic mulated over the past decade for industrial or commercial fragments 327, 427, and 527 were evident and were attributed applications are not expected to differ significantly with to the loss of -HF + H2O from the M + 1 molecular ion as

VOL. 40, NO. 5, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1449 FIGURE 2. GCMS chromatogram of sample obtained from purging of Teflon Advance Rug and Carpet Protector, a commercially available product designed for post-application carpet treatment. The telomer alcohols detected were 6:2, 8:2, 10:2, and 12:2 as identified by their mass spectra under positive chemical ionization (PCI) (inset) mode.

FIGURE 3. Profiles of residual unbound polyfluorinated alcohols detected in the seven fluorinated materials tested. Values are expressed as percent of total residuals measured. previously reported (27). In materials that contained 4:2 to be the predominant material identified in the Teflon FTOH, the molecular ion m/z 265 and characteristic fragment Advance (Figure 3) and polyfox-L-diol, the two known 227 were observed, although in materials that contained 12:2 telomer-based polymeric materials used in the study. This FTOH, molecular ion m/z 665 was the only familiar fragment is expected since it has been reported that telomer com- observed and the expected 627 was not evident. Analysis of pounds with carbon chain length equaling 10 (8 perfluori- telomer alcohols using electron impact ionization (EI) often nated carbons) is the key surface-active ingredient in fails to produce a strong signal for the molecular ion, typical polymeric materials (20). Contact angle is a physical property fragments observed however for these compounds are m/z critical in imparting repellency, where higher contact angles 69, 95, and 131 (28). This was evident when EI was used to decrease adhesion. It was reported that the contact angle verify the presence of FTOHs from the samples. achieved by polymers with a general structure of F(CF)2)n- Profiles of FTOHs removed from the other fluorinated (CH2)2O2C[C(CH3)-CH2]2 where the perfluorinated chain materials investigated differed, although 8:2 FTOH appears measures 8 carbons is optimal for water and soil repellency

1450 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 5, 2006 that are expected to preferentially partition into air due to TABLE 1. Total Residual Polyfluorinated Telomer Alcohols and their high vapor pressures and low water solubility (29). Sulfonamides Removed from Various Fluorinated Polymeric and Surfactant Materials Hence, the technique applied in this study is expected to be superior to more traditional solvent extraction methods of % of dry weight purification though it may not be applicable on an industrial of initial scale. fluorinated material fluorinated materiala Total masses of fluoro alcohols purged from headspace polyfox-L-diol 0.11b (0.03) of fluorinated polymers and surfactants studied ranged from Teflon Advance 0.34b (0.20) 0.04 to 3.8% on the basis of mass per dry mass of initial Zonyl FSO 100 1.03 (0.61) material (Table 1). In this investigation, variation was Zonyl FSE 3.80 (1.09) observed in three of the measured materials, Zonyl FSE, Zonyl 8:2 methacrylate monomer 0.04 (0.01) FSO 100, and Teflon Advance. This may be attributed to Motomaster Windshield Washer 0.36 (0.01) with Teflon nonhomogeneous consistency of materials tested. Both Zonyl Scotchgard Rug and Carpet Protector 0.39 (0.06) products were viscous aqueous dispersions that were resistant to mixing, while the Teflon advance product was milk-like a b Data are means (standard deviations). Average percentage of 6 in consistency. These values are in agreement with those experimental vessels. All other materials tested were measured in - triplicate. reported by 3M of residuals in concentration of being 1 2% or less in their final products (30). A study by Boulanger et al. (31), published after the initial submission of this manuscript, reported the measurement of residual fluori- nated monomers in a single electrochemical based surface protector product. The percent residuals reported are extremely low, which is not surprising since the dominant fluorinated material used in surface protection in this product line was the N-MethyFose alcohol (30); this dominant material was apparently not analyzed in their study. To assess the potential contribution of residuals to the overall flux of the telomer alcohols to the environment, key assumptions need to be made. First, values obtained from this study are conservative estimates since information is lacking concerning postproduction processing that the compounds may have undergone prior to handling in our FIGURE 4. Cumulative residual alcohols extracted versus days lab. It is probable that additional release of the volatile purged in Zonyl FSO 100, an ethoxylated nonionic fluorosurfactant. compounds occurred prior to packaging and shipping of the 4:2 FTOH is not adequately retained on the XAD cartridges used and various materials investigated in this study. On the basis of mass shown is a significant underestimation. manufacturing data in 2000-2002 telomer alcohols had an estimated global production of 5-6.5 × 106 kg yr-1 (20). This - × 6 -1 (17). This may explain the abundant use of the 8:2 FTOH in has increased to 11 14 10 kg yr (32) perhaps related to - various fluorinated polymeric materials. The monomer or the withdrawal by 3M of their POSF based products in 2000 the 8,2 methacrylate (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-hep- 2002 (2). tadecafluorodecyl methacrylate), tested consisted mainly of The method applied in this study was designed to the 8:2 FTOH as expected but it also contained small amounts efficiently force out the residual compounds from the of the shorter chain 6:2 FTOH. The relatively low percent materials tested. Actual rates of residual release to the residual (Table 1) is presumably due to the extensive environment are difficult to determine due to diverse separation steps required to isolate the 8:2 methacrylate from applications of these fluorinated products, yet undoubtedly the other chain length methacrylates likely generated in the the potential exists for a significant proportion of the residual synthesis. Zonyl FSO-100 and Zonyl FSE contained unbound fluoro alcohols to be released. Ellis et al. in their study of the 6:2 FTOH as the primary component of telomer alcohols atmospheric lifetime of telomer alcohols, have reported that purged; it has been reported that 6:2 FTOH is primarily based on crude calculations, a flux on the order of 100 000- incorporated into nonpolymeric, surfactant materials (20). 1 000 000 kg yr-1 is needed to maintain the concentrations The Motomaster Windshield Washer was shown to contain currently observed in the atmosphere (33). The data presented mostly the 6:2 FTOH; it may be that the surface-active in this paper suggests the residual fluoro alcohol contribution component of this consumer product is surfactant based to the atmospheric load of these chemicals is significant and rather than polymeric. may be the dominant source. Evidence supporting this is the This study demonstrated the effective removal of the reported measurement of the highest concentrations of these volatile compounds from fluorinated polymeric and sur- fluoro alcohols in Griffin, Georgia, a known hub for the carpet factant materials by air stripping. Figure 4 shows the manufacturing industry. An average of 148 pg m-3 of telomer relationship between accumulated telomer alcohols extracted alcohols and 403 pg m-3 of sulfonamido alcohols were versus days purged in vessels containing Zonyl FSO-100. The detected at this sampling location (2) although widespread majority of the volatile compounds investigated were stripped detection of these compounds was also observed throughout in less than 2 days and no significant increase in accumulation the North American atmosphere. This observation indicates was observed in subsequent days. For the other materials that release of residual fluoro alcohols may occur all along studied (results given in the Supporting Information) ac- the supply chain from production, through application, into cumulation of residuals ceased at various times from 1 day actual consumer use. These suppositions need verification for the 8:2 methacrylate, to 38 days for the Teflon Advance. by additional measurements inside and outside the manu- The method of continuous purging of the material while facturing plant as well as within areas containing the coated dispersed in water takes advantage of the inherent physical materials. Supportive of these data is the recent paper by properties of the fluorinated alcohols. Telomer and sulfona- Shoeib et al. reporting indoor air concentrations of fluorinated mido alcohols are considered to be hydrophobic compounds sulfonamidoethanol related chemicals (34).

VOL. 40, NO. 5, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1451 Removal of these volatile compounds from various (2) Stock, N. L.; Lau, F. K.; Ellis, D. A.; Martin, J. W.; Muir, D. C. G.; fluorinated materials is critical to reduce the occurrence of Mabury, S. A. Polyfluorinated telomer alcohols and sulfonamides fluoro alcohols in the atmosphere and ultimately minimize in the North American trophosphere. Environ. Sci. Technol. 2004, 38, 991-996. the contributions to perfluorinated acid accumulation in the (3) Ellis, D. A.; Martin, J. W.; De Silva, A. O.; Mabury, S. A.; Hurley, environment. The detection of the unbound alcohols from M. D.; Andersen, M. P. S.; Wallington, T. J. Degradation of the monomer “stage” of the process, as demonstrated by the fluorotelomer alcohols: A likely atmospheric source of per- presence of residuals from the methacrylate monomer fluorinated carboxylic acids. Environ. Sci. Technol. 2004, 38, studied here, show that perhaps these residuals are simply 3316-3321. a function of incomplete synthesis or poor purification at (4) Hurley, M. D.; Wallington, T. J.; Andersen, M. P. S.; Ellis, D. A.; Martin, J. W.; Mabury, S. A. Atmospheric chemistry of fluorinated the monomer step of the manufacturing process. A typical alcohols: Reactions with Cl atoms and OH radicals and synthetic reaction where fluorinated monomeric acrylates atmospheric lifetimes. J. Phys. Chem. A 2004, 108, 1973-1979. are produced using transesterification reaction of the 8:2 (5) Hurley, M. D.; Wallington, T. J.; Andersen, M. P. S.; Ellis, D. A.; FTOH along with ethyl pyruvate was reported to have an Martin, J. W.; Mabury, S. A. Atmospheric chemistry of 4:2 overall yield of 70% (35) indicating that unreacted material fluorotelomer alcohol: Products and mechanism of Cl atom - may still be present if left unpurified. Elimination of un- initiated oxidation. J. Phys. Chem. A 2004, 108, 5635 5642. (6) Dinglasan, M. J.; Ye, Y.; Edwards, E. A.; Mabury, S. A. Fluo- reacted alcohols at this stage in the manufacturing process rotelomer alcohol biodegradation yields poly- and perfluori- will reduce the amounts present at the polymerization step, nated acids. Environ. Sci. Technol. 2004, 38, 2857-2864. assuming that the polymerization reaction itself does not (7) Wang, N.; Szostek, B.; Folsom, P. W.; Sulecki, L. M.; Capka, V.; cleave the linkage between the fluorinated alcohols and the Buck, R.; Berti, W.; Gagnon, J. Aerobic biotransformation of polymeric backbone. 14C-labeled 8-2 telomer B alcohol by activated sludge from a domestic sewage treatment plant. Environ. Sci. Technol. 2005, This study indicates the potential for a significant amount 39, 531-538. of fluorinated alcohols to be released as residuals from a (8) Kennedy, G. L., Jr.; Butenhoff, J. L.; Olsen, G. W.; O’Connor, J. suite of fluorinated materials that are industrially applied C.; Seacat, A. M.; Perkins, R. G.; Biegel, L. B.; Murphy, S. R.; and commercially available and hence contribute substan- Farrar, D. G. The toxicology of perfluorooctanoate. Crit. Rev. tially to the atmospheric burden of FTOHs. The ability of Toxicol. 2004, 34, 351-384. these compounds to undergo long-range atmospheric trans- (9) Biegel, L. B.; Hurtt, M. E.; Frame, S. R.; O’Connor, J.; Cook, J. C. Mechanism of extrahepatic tumor induction by peroxisome port provides a means to the production of PFCAs in the proliferators in male rats. Toxicol. Sci. 2001, 60,44-55. environment as they degrade. This study also suggests that (10) Lau, C.; Butenhoff, J. L.; Rogers, J. M. The developmental toxicity direct exposure of the general population to these compounds of perfluoroalkyl acids and their derivatives. Toxicol. Appl. is plausible if these materials are applied in homes and are Pharmacol. 2004, 198, 231-241. outgassing after treatment of surfaces, including carpet, (11) Hagen, D. F.; Belisle, J.; Johnson, J. D.; Venkateswarlu, P. textiles, or paper products. Metabolism of these volatile Characterization of fluorinated metabolites by a gas chromato- graphic-helium microwave plasma detector - the biotrans- precursors would then lead to the perfluorinated acids formation of 1H,1H,2H,2H - perfluorodecanol to perfluorooc- detected in human blood samples worldwide. The elimina- tanoate. Anal. Biochem. 1981, 118, 336-343. tion of these precursor compounds from marketed fluori- (12) Martin, J. W.; Mabury, S. A.; O’Brien, P. J. Metabolic products nated materials would appear to significantly reduce the likely and pathways of fluorotelomer alcohols in isolated rat hepa- production of perfluorinated acids in the environment; in a tocytes. Chem. Biol. Interact. 2005, 155, 165-180. recent presentation to the Environmental Protection Agency, (13) Desilva, A. O.; Mabury, S. A. Isolating isomers of perfluorocar- boxylates in polar bears (Ursus maritimus) from two geo- a leading manufacturer of telomer based-materials has graphical locations. Environ. Sci Technol. 2004, 38, 6538-6545. announced the removal of residuals from their products by (14) Shoeib, M.; Harner, T.; Ikonomou, M.; Kannan, K. Indoor and 2006 (32). Studies are underway in our laboratory to outdoor air concentrations and phase partitioning of perfluo- determine whether abiotic and biotic degradation of poly- roalkyl sulfonamides and polybrominated diphenyl ethers. meric materials and surfactants, post-application, can release Environ. Sci. Technol. 2004, 38, 1313, 1320. additional fluoro alcohols to the environment. (15) Xu, L.; Krenitsky, D. M.; Seacat, A. M.; Buttenhoff, J. L.; Anders, M. W. Biotransformation of N-ethyl-N-(2-hydroxyethyl)per- fluorooctanesulfonamide by rat liver microcosomes, cytosol, Acknowledgments and slices and by expressed rat and human cytochromes P450. - We acknowledge NSERC for a strategic grant and Hira Syed Chem. Res. Toxicol. 2004, 17, 767 775. for her assistance in sample preparation. (16) Giesy, J. P.; Kannan, K. Global distribution of perfluorooctane sulfonate in wildlife. Environ. Sci. Toxicol. 2001, 35, 1339-1342. (17) Kissa, E. Fluorinated Surfactants and Repellents; Surfactant Note Added after ASAP Publication Science Series 97; Marcel Dekker: New York, 2001. This article was published ASAP on January 25, 2006; a revision (18) Giacobbi, E.; Scialla, S.; Stiros, P. (Procter and Gamble). Composition and Methods for Treating Surfaces. U.S. Patent to the POSF paragraph in the Results and Discussion section 20020142097A1, 2002. appears in the version published ASAP on February 3, 2006. (19) Moody, R. After-treatment method for imparting oil-and-water- repellency to fabric. U.S. Patent 6,165,545, 2000. Supporting Information Available (20) Telomer Research Program. Telomer Research Program Update, Presented to the USEPA OPPT, November 25, 2002; U.S. Further information regarding the experimental setup, blank Environmental Protection Agency public docket AR226-1141. samples, spike and recovery data, amounts of fluorinated (21) Falco, M. 3M Corp. Personal communication, July 19, 2005. alcohols measured, average dry weights of fluorinated (22) Material Safety Data Sheet for Teflon Advance Carpet Protector; materials, and plots of accumulated alcohols removed versus DuPont Canada, Inc.: Mississauga, ON, 2001. days for the other fluorinated materials investigated. This (23) Material Safety Data Sheet for Scotchgard Carpet and Rug material is available free of charge via the Internet at http:// Protector, ID 09-3245-9; 3M Corp.: London, ON, 2003. (24) DuPont Zonyl FSO-100 Product Information Sheet. pubs.acs.org. (25) DuPont Zonyl FSE Product Information Sheet. (26) Kausch, C.; Leising, J. E.; Medsker, R.; Russell, V.; Thomas, R. R. Synthesis, characterization, and unusual surface activity of Literature Cited a series of novel architecture, water-dispersible poly(fluoroox- (1) Martin, J. W.; Muir, D. C. G.; Moody, C. A.; Ellis, D. A.; Kwan, etane)s. Langmuir 2002, 18, 5933-5938. W. C.; Solomon, K. R.; Mabury, S. A. Collection of airborne (27) Ellis, D.; Mabury, S. A. Chemical ionization pathways of fluorinated organics and analysis by gas chromatography/ polyfluorinated chemicals - A connection to environmental chemical ionization mass spectrometry. Anal. Chem. 2002, 74, atmospheric processes. J. Am. Soc. Mass Spectrom. 2003, 14, 584-590. 1177-1191.

1452 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 5, 2006 (28) Napoli, M.; Krotz, L.; Scipioni, A. Mass spectrometry of some (33) Ellis, D.; Martin, J. W.; Mabury, S. A.; Hurley, M. D.; Sulbaek C6F13-compounds and their C6H13-analogues. Rapid Commun. Andersen, M. P.; Wallington, T. J. Atmospheric lifetimes of Mass Spectrom. 1993, 7, 789-794. fluorotelomer alcohols. Environ Sci Technol. 2003, 37, 3816- (29) Lei, Y. D.; Wania, F.; Mathers, D.; Mabury, S. A. Determination 3820. of vapour pressures, octanol-air, and water-air partition (34) Shoeib, M.; Harner, T.; Wilford, B. H.; Jones, K. C.; Zhu, J. coefficients for polyfluorinated sulfonamide, sulfonamidoet- Perfluorinated sulfonamides in indoor and outdoor air and hanols, and telomer alcohols. J. Chem. Eng. Data 2004, 49, 1013- indoor dust: occurrence, partitioning, and human exposure. 1022. Environ. Sci. Technol. 2005, 39 (17), 6599-6606. (30) Fluorochemical Use, Distribution and Release Overview; prepared (35) Guyot, B.; Ame´duri, B.; Boutevin, B.; Side´ris, A. Synthesis and by the 3M Company for USEPA OPPT, May 26, 1999; U.S. polymerization of fluorinated acrylic monomers substituted in Environmental Pretection Agency public docket AR226-0550. R-position. 4. Applications to 2-perfluorooctylethyl R-acetoxy- R (31) Boulanger, B.; Vargo, J. D.; Schnorr, J. L.; Hornbuckle, K. C. acrylate and -propionyloxyacrylate. Macromol. Chem. Phys. - Evaluation of perfluorooctane surfactants in a wastewater 1995, 196, 1875 1886. treatment system and in a commercial surface protection product. Environ. Sci. Technol. 2005, 39 (15), 5524-5530. Received for review August 15, 2005. Revised manuscript (32) DuPont Global PFOA Strategy - Comprehensive Source Reduc- received November 8, 2005. Accepted December 16, 2005. tion; presented to the USEPA OPPT, January 31, 2005; U.S. Environmental Protection Agency public docket AR226-1914. ES051619+

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