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-fT f^A fLG 106/ *rr Monitoring PerRuorinated Surfactants in Biota and Surface Water Sam ples Following an Accidental Release of Fire-Fighting Foam into Etobicoke Creek C H E R Y L A. M O O D Y , t J O N A T H A N W. M A R T I N , 1 WAI CHI K W A N , 1 DEREK C. G. M U IR ,4 AND S C O T T A. M A B U R Y * 1 Department o f Chemistry, 80 St. George Street, University o f Toronto, Toronto, Ontario, Canada M5S 3H6, Department o f Environmental Biology, University o f Guelph, Guelph, Ontario, Canada N IG 2W1, and National Water Research Institute, Environment Canada, 867 Lakeshore Road, Burlington, Ontario, Canada L7R 4A6 TABLE 1. Examples of Parfluoriiited Snrfactants with Acronyms snd Molecnlar Formulas compound molecular acronym formula perfluoroalkanesulfonates perfluorooctanesulfonate anion perfluorohexanesulfonate anion perfluorobutanesulfonate anion perfluorocarboxylates perfluorotetradecanoic acid anion perfluorododecanoic acid anion perfluoroundecanoic acid anion* perfluorodecanoic acid anion perfluorononanoic acid anion* perfluorooctanoic acid anion perfluoroheptanoic acid anion perfluorohexanoic acid anion perfluoropentanoic acid anion PFOS PFHxS PFBS PFTA PFDoA PFUnA PFDA PFNA PFOA PFHpA PFHxA PFPeA CaFi7S03C6FiaS03~ c *f 9s o 3- C i 3F27C O O CitF23COO~ CioFaiCOO" CsF^COO" CsFuCOOC7F15C O O c 6f 13c o o C 5F11C O O C4F9COO- C o m p o u n d em ployed as an internal standard for study. Perfluorinated surfactants have emerged as priority environmental contaminants due to recent reports of their detection in environmental and biological matrices as well as concerns regarding their persistence and toxicity. In June 2000, 22000 L of fire retardant foam containing perfluorinated surfactants was accidentally released at L. B. Pearson International Airport, Toronto, ON, and subsequently entered into Etobicoke Creek, a tributary to Lake Ontario. A suite of analytical tools that include liquid chromatography/tandem mass spectrometry (LC/MS/MS) and ,SF N M R were employed to characterize fish (common shiner, Notropus cornutus) and surface water samples collected following the discharge of the perfluorinated material. Total perfluoroalkanesulfonate (4,6, and 8 carbons) concentrations in fish liver samples ranged from 2.00 to 72.9 /zg/g, and total perfluorocarboxylate (5-14 carbons) concentrations ranged from 0.07 to 1.02 /zg/g. In addition to fish samples, total perfluoroalkanesulfonate (6 and 8 carbons) concentrations were detected in creek water samples by LC/MS/MS over a 153 day sampling period with concentrations ranging from <0.017 to 2260 /zg/L; perfluorooctanoate concentrations (<0.009-11.3 /zg/L) were lower than those observed for the perfluoroalkanesulfonates. By ,9F NMR, the total perfluorinated surfactant concentrations in surface water samples ranged from <10 to 17000/zg/L. A bioaccumulation factor range of 6300-- 125000 was calculated for perfluorooctanesulfonate, based on concentrations in fish liver and surface water. The residence time of PFOS in Etobicoke Creek as well as the high bioaccumulation in fish liver suggests that perfluorinated surfactants will persist and bioaccumulate fallowing release into the aquatic environment. * Corresponding author phone: (416) 978-1780; fax: (416) 9783596; e-mail: smabury@>chem.utorontoxa. 1University o f Toronto. * University of Guelph. 4 National Water Research Institute. Introduction Concerns regarding the environmental persistence and the potential for bioaccumulation of two anionic perfluorinated surfactants--perfluorooctanesulfonate (PFOS, Table 1) and perfluorooctanoic acid (PFOA, Table 1)--prompted the primary manufacturer to phase out their production (1-4). The decision by the primary manufacturer to reduce production o f commercial products was due in part to the detection o f PFOS concentrations (10--100/zg/L) in human blood samples from the United States, Japan, Europe, and China (2, 5) and in biota samples (1, 6, 7). The PFOS concentrations measured in a variety of biota and environ mental samples have raised questions concerning the mechanism(s) for their widespread dissemination o f PFOS. Perfluorinated surfactants are employed for industrial and commercial applications and are used in lubricants, paints, polishes, food packaging, and fire-fighting foams (8-11). PFOS is an important perfluorinated surfactant as well as a precursor to other perfluorinated surfactants (12). In 2000, the estimated annual U .S. production quantity of PFOS was 2,943,769 kg, and as a result of the primary manufacturer's phase out, the anticipated 2003 annual U .S. PFOS production will be 0 kg (13). Perfluoroalkanesulfonate salts and perfluorocarboxylates are present in fire-fighting foam formulations, including aqueous film forming foam s (AFFFs) (14, 15). AFFFs are proprietary mixtures used to extinguish hydrocarbon fuel fires and are often found where there are large volumes of flammable liquids and the potential for a fire exists. For example, AFFFs are found at U .S . military bases, fire departments, and airports (14). Other components of AFFFs include diethylene glycol butyl ether, hydrocarbon surfac tants, and corrosion inhibitors (14). Years of employing AFFFs in a variety o f situations has resulted in these fire-fighting foam components being directly released to the environment and the contamination of groundwater (14, 16-22). Historically, perfluorinated surfactants, including PFOS and PFOA, were detected by nonspecific methods (23-25) such as the oxyhydrogen torch method (26). Employing liquid chromatography/mass spectrometry (LC/MS) permitted the compound-specific detection of perfluorinated surfactants in abiotic and biotic matrices (5,14). Recently, concentrations of PFOS, perfluorohexanesulfonate (PFHxS, Table 1), PFOA, 10.1021/es0110Ql+ CCC: $22.00 O xxxx American Chemical Society Published on W eb 00/00/0000 PAG E EST: 6.8 VOL. xx, NO. xx, xxxx / ENVIRON. SCt. 8c TECHNOL. A PO ro to C O N T A IN N O I FIGURE 1. M ap of study region Indicating location of Etoliicoka Creak, fish and surface water sample sites, and la k e Ontario. and perfluorooctanesulfonylamide were reported in 65 nonoccupationally exposed human sera samples by liquid chromatography/tandem mass spectrometry (LC/MS/MS), with PFOS concentrations ranging from 6.7 to 81.5^g/L (271. U sing similar LC/MS/MS methodologies, PFOS concentra tions were measured in liver and sera o f wildlife species (6, 7 ,28); some of the highest concentrations o f PFOS from the data sets (6) were observed in bald eagle serum (n = 26. average = 360 ng/mL) and mink liver tissue (n = 18, average = 2630 ng/g). In addition to PFOS concentrations present in biological matrices, a limited number of measurements of surface water concentrations by LC/MS/MS have been reported. For example, two Alabama sample locations in Decatur and Mobile had surface water concentrations ranging from the method quantitation limit (25 ng/L) to 114 ng/L (29). Surface water sampled near a Columbus, GA, water works' facility contained maxim um PFOS concentrations of 83.3 ng/L(29). Both surface water sampling locations were in the proximity of perfluorinated surfactant-related manufacturing facilities (29), and because o f the proximity to such facilities, the PFO S concentrations may not necessarily be indicative of back ground concentrations. The characterization of Etobicoke Creek (Toronto, ON) was initiated the day after an accidental release of a multiple perfluorinated surfactant fire-fighting foam product. The aim of this investigation was to determine perfluoroalkanesulfonate and perfluorocarboxylate concentrations and evaluate their residence time and long-term fate in Etobicoke Creek. Specifically, in this paper, we detail (1) perfluoroalkanesulfonate and perfluorocarboxylate concentrations by LC/MS/MS in biota and surface water samples collected from Etobicoke Creek and (2) total perfluorinated surfactant concentrations in surface water samples collected from Etobicoke Creek by ,9F NMR. B ENVIRON. SCI. 8i TECHNOL. / V O L xx, NO. xx, xxxx Experimental Section Standards and Reagents. Standards of potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate (99.9%), and potassium perfluorooctanesulfonate (86.4%) were provided by the 3M Co. Standards ofperfluoropentanoic acid (PFPeA, 97%), perfluoroheptanoic acid (PFHpA, 99%), PFOA (98%), perfiuorononanoic acid (PFNA, 97%), perfluorodecanoic acid (PFDA, 98%), perfluoroundecanoic acid (PFUnA, 95%), perfluorododecanoic acid (PFDoA, 95%), perfluorotetradecanoic acid (PFTA, 97%), and perfluoro octanesulfonate tetraethylammonium salt (98%) were pur chased from Aldrich Chem ical Co. (Milwaukee, WI), and perfluorohexanoic acid (PFHxA, 95%) was obtained from Oakwood Research Chemicals (West Colum bia, SC). A m monium acetate (98%) and tetrabutylammonium hydrogen sulfate (TBAS) were purchased from Aldrich Chem ical Co., anhydrous sodium carbonate (99.8%) was purchased from J. T. Baker (Phillipsburg, NJ), and methyl rert-butyl ether (MTBE) was purchased from EM Science (99.5%, Gibbsburg, NI). The 19F NM R internal standard, 4'-(trifluoromethoxy)acetanalide (TFMAA), N M R solvent methyl-d* alcohol, and chromium acetyiacetonate were purchased from Aldrich Chemical Co. (Mississauga, ON , Canada). All reagents and solvents were used as received. Spill Description and Environm ental Conditions. On June 8,2000, a fire alarm malfunctioned at an airline hanger at the L. B. Pearson International Airport, Toronto, ON, Canada. The malfunction released 22000 L of fire retardant foam and 450000 L o f water from the sprinkler system into storm sewers, leading to Spring Creek (approximate travel distance of 1.8 km) and subsequently to Etobicoke Creek, which empties into Lake Ontario (Figure 1) (22). The approximate travel distance of the released material from the airport to Lake Ontario was 15 km. An AFFF Material Safety Data Sheet (MSDS) (J5) for a compound similar in composition to the AFFF material used at the airport states that perfluoroalkanesulfonate salts comprise 0.5-1.5% o f the AFFF concentrate formulation. With the volume released (22000 L) and the approximate density o f the concentrate equal to 1g/mL Q5), the quantity o f perfluoroalkanesulfonate salts released into the environ ment from this spill ranged from 110 to 330 kg. Residual organofluorochemicals, which perfluorocarboxylates are believed to be one of, comprise < 1% o f AFFF formulations (15). On the basis o f M SDS information (15), the total estimated quantity of perfluorinated compounds, including anionic and amphoteric perfluorinated surfactants, released into the environment from this spill was 330--1650 kg. For the month o f June, a precipitation monitoring station at the airport measured a total o f 169.2 mm of rain. From June 8 (date of spill) to June 29,2000 (21 days after spill), the total rainfall was 163.2 mm. Additionally, several storm sewers for the city of Mississauga, ON, empty into Etobicoke Creek, therefore increasing the volume o f water in Etobicoke Creek. The water levels and flow rate obtained from a monitoring station located ~2 km south of sample site 5 (Figure 1) were used to estimate the volume of water in Etobicoke Creek during June. Sam ple Collection. O n June 29, 2000, fish samples (denoted airport 1--6) were electroshocked and collected within L. B. Pearson International Airport property. Additional fish were collected on January 4, 2001; two minnow traps were placed north of the airport and the spill, and three were placed south o f the airport (near sample site 2; Figure 1). The traps were retrieved on January 5,2001, with one fish (denoted upstream 1) collected from the north site and two fish (combined into one sample denoted downstream 1) collected from the southern location. All fish collected were identified as common shiner (Notropus cornutus) and weighed from 3 to 8 g. Only the liver tissues were used for analyses because previous, preliminary Findings indicated PFOS accumulated in liver tissue (30). Tissues were analyzed immediately after sampling or kept frozen prior to analysis. It has been reported that perfluoroalkanesulfonates and perfluorocarboxylates may adsorb to glass (31); therefore, all surface water samples were collected in high-density poly ethylene bottles. Surface water samples were collected over a period o f three weeks after the spill; an additional suite of samples was collected November 8, 2000. Sample site 1 (Figure 1), which is upstream of the airport and the AFFF spill, was collected as background surface water. The surface water samples were grab samples from midchannel and stored without preservation at 4 "C prior to analysis. For sampling protocol and methodologies, care was taken to avoid sample contact with Teflon, which is known to contain one or more of the analytes of interest (21). Biota Sam ple Analysis by LC/MS/MS. Fish livers (50-- 100 mg) were isolated and homogenized in 2 -3 m L o f 0.25 M sodium carbonate and 1mL of 0.5 M TBAS to disrupt cells and form the respective ion pairs (27). The aqueous hom o genate was shaken twice for 10 min with 5 m L aliquots of MTBE; the com bined MTBE extracts were taken to dryness with Nz and reconstituted in 1- 2 m L o f50:50 water/methanol. Each sample was filtered (0.2/rmnylon filters) prior to analysis by LC/MS/MS. Perfluoroalkanesulfonate and perfluorocarboxylate concentrations in fish tissue extracts were deter mined by LC/MS/MS.employing instrumental conditions similar to those described in Moody et al. (32). Quantitation was performed by standard curve analysis o f spiked water samples extracted in the same manner as the fish tissue, with PFNA or PFDoA employed as the internal standard. Fish liver tissue recoveries for all target analytes were quantitative (>80%) (33). Aqueous blanks and matrix blanks (100 mg of farm-raised rainbow trout liver) were analyzed simultaneously with each set of tissue samples to monitor for contamination. The method detection limits were defined as 3.6 and 1.2 ng/g for PFOS and PFOA, respectively, for a 100 m g wet weight liver tissue sample. Surface Water Analysis by LC/MS/MS. Perfluoroalkane sulfonate and perfluorooctanoate concentrations in surface water were measured according to the method of M oody et al. (32). Briefly, solid phase extraction cartridges (C-18) were used to extract perfluoroalkanesulfonates and perfluoro carboxylates from surface water (0.2-200 mL). The analytes were eluted from the cartridges with methanol, chromato graphed using HPLC with a flow rate of 300 /rL/min, and analyzed by negative electrospray ionization LC/MS/MS. For quantification of each compound, multiple reaction moni toring was employed. The detection limit of the method was defined as those concentrations of PFOS and PFOA needed to produce a signal-to-noise ratio (S/N) o f 3:1. The instru mental detection limits were 4 and 1pg for PFOS and PFOA, respectively (32). Method limits o f quantitation for a 100 m L surface water sample by LC/MS/MS were 17 and 9 ng/L for PFOS and PFOA, respectively. Quantification o f PFHxS was performed by assuming a response factor equal to an equimolar amount of PFOS. Surface Water Analysis by " F NM R. Total perfluorinated surfactant concentrations were measured using the ,9F NM R method of Moody et at. (32). To summarize, the surface water samples (2-100 mL) were preconcentrated by employing solid phase extraction (C-18), and the analytes of interest were eluted with deuterated methanol and then analyzed by solution 19F NM R. Spectra were obtained on a Varian Unity 500, three-channel spectrometer operating at 470.297 mHz at 26 C. Optimized parameters included the 90" pulse width of 10.5 s and the spectral window o f -5 0 to -8 5 ppm. The total concentration of perfluorinated surfactants, which include PFOS, PFHxS, and PFOA, was determined by external calibration using known concentrations o f PFOS and 4'(trifluoromethoxyjacetanalide. O n the basis o f an S/N o f 3:1, the instrument detection limit was 0.25ftg/mL. The detection limit o f the method was defined as those concentrations of PFOS needed to produce an S/N of 3:1 and was 10 ftg/L for a 100 m L surface water sample. Results a n i D iscission Etobicoke Creek Biota Samples. Nine fish liver tissue samples collected from Etobicoke Creek were analyzed for perfluo roalkanesulfonates and perfluorocarboxylates. Because of their small size, two liver tissue samples collected near sample site 2 in January 2001 were pooled (sample denoted downstream 1). Blank liver tissue (farm-raised rainbow trout) contained no detectable concentrations of perfluoroalkane sulfonate or perfluorocarboxylate homologues. A typical chromatogram indicates the presence of multiple perfluorinated compounds in extracted fish liver tissue (Figure 2) and clearly illustrates the homologue patterns observed for perfluoroalkanesulfonates and perfiuorocarboxylates. PFNA, m/z 463, or PFDoA (m/z 613, Figure 2) was employed as the internal standard for quantification; there fore, no exposure data are reported for either o f these compounds. Total perfluoroalkanesulfonate concentrations in fish liver tissue ranged from 2.00 to 72.9 /tg/g (Table 2). PFOS was detected in each fish liver sample and was the predominant homologue, comprising >99% of the total perfluoroalkane sulfonate concentration. The concentrations of two smaller chain perfluoroalkanesulfonate homologues were signifi cantly lower than PFOS concentrations; PFHxS concentra tions were detected in sue of the eight samples, ranging from 0.011 to 0.29fig/g, and PFBS was detected in only two samples, at concentrations o f0.0090 and 0.0077/ig/g. The fish sample collected upstream of the airport, and the AFFF spill, had detectable concentrations of PFOS and PFHxS, 9.19 and 0.046 Hg/g, respectively. VOL. xx. NO. xx, xxxx I ENVIRON. SCI. & TECHNOl. C 3 too- PFTA ----------------- ------------------------------------- -- COD 100] OcJ O c 100-1 -DQ < tC0 " 1 0 Q. 1 - PFDoA * internal Standard A . a PFUnA _______ A . PFDA ^ PFOS ^ PFOA 100) P F H x S V 100. A . PFHpA 10.00 10.SC 11.06 1140 13.00 1J.S0 13.00 1S0 713 >669 813 >569 563 >519 513 >469 499 >99 413 >369 399 >99 363 > 319 Tim e (min) H G U R E 2. Typical LC/MS/MS chromatogram of fish livar extract (sample identification: airport 4) collected dow nsiraam of the AFFF spill. The numbers listed at the right of each trace represent the parent ion (mb) and the daughter ion [ m M transition monitored for quantification. TABLE 2. Individual Perfinoroalkanesulfonate Homologue Concentrations in Fish Livor Tissue by LC/MS/MS sample ID* sample data PFBS PFHxS PFOS total (/'g/g) O '9/8) 0<9/9) O '9/9 ) airport 1 June 29, 2000 airport 2 June 29, 2000 airport 3 June 29,2000 airport 4 June 29,2000 airport 5 June 29,2000 airport 6 June 29, 2000 upstream 1 Jan 5, 2001 downstream 1 Jan 5, 2001 nd* nd nd nd 0.0090 0.0077 nd nd 0.011 nde nd 0.011 0.062 0.028 0.046 0.29 72.9 2.00 32.4 9.85 30.0 12.0 9.19 39.9 72.9 2.00 32.4 9.86 30.1 12.0 9.23 40.2 Airport sam ple s collected w ithin the boundaries o f 1. B. Pearson International Airport,Toronto,ON, Canada. * nd denotesnondetectable. The detection limit for P F B S w a s 0.0038/g/g for a 100 m g wet weight tissue sam p le .e nd denotes nondetectable. The detection limit for PFH xS w a s 0.0023/g/g for a 100 m g wet w eight tissue s a m p le .d Dow nstream 1 concentration represents tw o pooled liver Tissue sam ples. Total perfluorocarboxylate concentrations in fish liver tissues ranged from 0.070 to 1.02 //g/g, with an average concentration o f 0.385 //g/g (Table 3). The higher chain perfluorocarboxylate homologues (i.e., PFDA) were pre dominant in the fish liver tissues, where PFDA concentrations comprised 23-46% of the total concentration. In previous surfactant studies higher chain homologues {i.e., 14 carbons) of hydrocarbon surfactants partitioned into fish liver tissues at higher concentrations than lower chain homologues (34). The fish liver tissue collected north of the airport and the spill (upstream 1) had detectable concentrations of perfluorocarboxylates (PFHpA to PFTA), and the source(s) for these perfluorocarboxylates is(are) uncertain. Etobicoke Creek Surface Water Sample Analysis by LC/ MS/MS. Fifty-four surface water samples were collected from Etobicoke Creek and analyzed for perfiuoroalkanesulfonates and perfluorocarboxylates by LC/MS/MS. A chromatogram of PFOS, PFHxS, and PFOA (preconcentrated from surface water) was similar to those perfluorinated compounds extracted from fish liver tissues (Figure 2) and previously analyzed AFFF concentrates (32). The surface water samples from Etobicoke Creek had total perfluoroalkanesulfonate concentrations from nondetectable (nd; ~ <0.017 //g/L) to 2260 /ig/L, with PFOS concentrations ranging from nd to 2210 //g/L (Table 4). Other perfluoroalkanesulfonate hom o logues observed in surface water samples, but not quantified, included perfluoroheptanesulfonate and PFBS. PFOA concentrations ranged from nd (~ <0.009 //g/L) to 11.3 //g/L (Table 4). Lower chain perfluorocarboxylate ho mologues, including PFHpA, PFHxA, and PFPeA, were observed qualitatively. It should be noted that PFOA was detected in surface water samples that were collected upstream o f the AFFF spill at sample site 1, with a mean concentration o f 0.02 //g/L (Figure 3a). The highest PFOS, PFHxS, and PFOA concentrations were detected in surface water samples collected 1 day after the AFFF spill occurred (with the exception o f sample site 6, Table 4). The response o f PFOS, PFHxS, and PFOA concen trations with time at sample site 4, which is ~8 km from the airport, is shown in Figure 3b,c. A small increase in concentration o f total perfiuoroalkanesulfonates and PFOA was observed in surface water samples collected 21 days after the AFFF spill. Surface water samples that were collected in November 2000 (153 days after the initial spill) contained detectable concentrations o f PFOS and PFOA. Plausible reasons for the continued presence of perfluorinated sur factants in Etobicoke Creek include additional releases of AFFF materials from fire-training exercises within the Eto bicoke Creek region; residential, commercial, and industrial discharges to the creek; sediment sorption/desorption; and/ or hyporeiczone/bankstorage and release. Additionally, AFFF concentrate that remained in pipes and on other airport surfaces after the June 2000 spill may have been mobilized during large precipitation events. The PFOA concentrations (nd-0.02 //g/L) present in surface water samples collected 153 days after the spill were similar to those levels measured in Etobicoke Creek water collected upstream of the airport at sample site 1 (Figure 3a). TABLE 3. Individnal Perfluorocarboxylate Homologue Coiceutrations in Fish Liver Tissues by LC/MS/MS sample ID* airport 1 airport 2 airport 3 airport 4 airport 5 airport 6 upstream 1 downstream 1d sample date June 29, 2000 June 29, 2000 June 29, 2000 June 29, 2000 June 29, 2000 June 29, 2000 Jan 5, 2001 Jan 5, 2001 PFPeA (pg/g) 0.0046 nd6 0.0047 nd 0.013 0.0091 nd nd PFHxA (//g/g) 0.020 ndc 0.010 0.0033 0.040 0.027 nd nd PFHpA (//g/g) 0.016 0.0046 0.010 0.0082 0.048 0.038 0.10 0.11 s' 3 li 0.011 0.0060 0.0086 0.011 0.040 0.036 0.08B 0.091 PFDA (/<g/g) 0.048 0.032 0.045 0.067 0.13 0.14 0.19 0.39 PFUnA (AD/g) 0.029 0.013 0.036 0.067 0.093 0.083 0.18 0.24 PFTA O '9/9) 0.0099 0.014 0.012 0.0088 0.029 0.034 0.25 0.19 total O/9/9) 0.14 0.07 0.13 0.16 0.40 0.36 0.82 1.02 * A irport sam p le s collected within the boundaries of L. B. Pearson International Airport, Toronto, O N , Canada. * nd denotes nondetectable. The detection limit for P FPe A w a s 0.0024 /<g/g for a 100 m g wet w eight tissue sam ple. * nd denotes nondetectable. T he detection limit for P F H xA w a s 0.0022 /g/g for a 100 m g w et w eight tissue sam ple. a D ow nstre am 1 concentration represents tw o pooled liver tissue sam ples. D ENVIRON. SCI. & TECHNOl. / VOL. xx, NO. xx, xxxx TABU 4. PFHxS, PfOS, m i PFOA Conceatrations a Sarface Water Samples by LC/MS/MS sample ID PFHxS PFOS* PFOA* total sample date n (pg/U (/.g/l) 0<b/1) t/egA.) sample 1-1 June 9, 2000 1 ndc sample 1-2 June 9, 2000 1 71.5 sample 1-3 June 9, 2000 1 134 sample 1-4 June 9, 2000 1 121 sample 1-5 June 9, 2000 1 ncd sample 1-6 June 9,2000 1 nd sample 2-1 June 10, 2000 1 nd sample 2-2 June 10, 2000 1 3.45 sample 2-3 June 10.2000 1 nd sample 2-4 June 10,2000 3 5.44 sample 2-5 June 10,2000 1 8.22 sample 2-6 June 10,2000 1 49.6 sample 3-1 June 11,2000 1 nd sample 3-2 June 11,2000 1 nd sample 3-3 June 11, 2000 3 3.44 sample 3-4 June 11,2000 1 1.47 sample 3-5 June 11, 2000 1 5.74 sample 3-6 June 11,2000 3 nd sam ple 6-1 June 1, 2000 1 nd sample 6-2 June 14, 2000 1 0.018 sam ple 6-3 June 14, 2000 1 0.042 sample 6-4 June 14, 2000 1 0.83 sample 6-5 June 14, 2000 1 0.22 sample 6-6 June 14, 2000 1 0.14 sample 9-1 June 17, 2000 1 nd sample 9-2 June 17, 2000 1 0.67 sample 9-3 June 17, 2000 1 0.023 sample 9-4 June 17, 2000 1 0.027 sam ple 9-5 June 17, 2000 1 0.11 sample 9-6 June 17, 2000 1 nd sam ple 13-1 June 21. 2000 1 nd sam ple 13-2 June 21, 2000 1 0.034 sample 13-3 June 21, 2000 1 0.035 sample 13-4 June 21,2000 1 0.046 sam ple 13-5 June 21, 2000 1 0.079 sample 13-6 June 21. 2000 1 0.12 sam ple 17-1 June 25, 2000 1 nd sam ple 17-2 June 25, 2000 1 nd sample 17-3 June 25, 2000 1 nd sample 17-4 June 25, 2000 1 nd sample 17-5 June 25, 2000 1 nd sample 17-6 June 25, 2000 1 nd sample 21-1 June 29, 2000 1 nd sample 21-2 June 29, 2000 1 0.024 sample 21-3 June 29, 2000 1 0.042 sample 21-4 June 29, 2000 1 0.23 sample 21-5 June 29, 2000 1 0.42 sample 21-6 June 29, 2000 1 0.091 sample 21* June 29,2000 1 0.051 sample 153-1 N o v 8, 2000 1 nd sample 153-2 N ov 8. 2000 1 nd sample 153-3 N ov 8, 2000 1 nd sample 153-4 N ov 8. 2000 1 nd sample 153-5 N ov 8, 2000 1 nd sample 153-6 N ov 8, 2000 1 nd nd 739 950 995 nc 0.16 nd 89.2 113 126 174 2210 nd 1.73 201 66.7 56.6 nd nd 0.55 0.63 9.11 2.51 2,66 nd 0.95 0.55 0.62 1.21 0.55 nd 0.34 0.45 0.48 0.48 0.91 nd 0,33 0.36 0,96 0.41 0.48 nd 0.33 0.56 4.39 3.23 1.18 1.49 nd 0.28 0.35 0.44 0.33 0.19 0.022 4.68 9.82 10.6 nc 0.035 0.011 0.81 0.61 1.60 2.49 11.3 0.028 0.19 0.51 1.14 1.89 nd 0.013 0.055 0.068 0.16 0.043 0.057 0.033 0.047 0.049 0.070 0.043 0.033 0.008 0.048 0.054 0.063 0.036 0.047 0.017 0.043 0.046 0.073 0.048 0.045 0.024 0.075 0.083 0.19 0.11 0.022 0.040 nd nd 0.02 0.02 0.02 0.02 0.022 815 1090 1130 nc 0.20 0.011 93.5 114 133 185 2270 0.028 1.92 205 69.3 64.2 nd 0.013 0.62 0.74 10.1 2.77 2.86 0.033 1.67 0.62 0.72 1.36 0.58 0.008 0.42 0.54 0.59 0.60 1.08 0.017 0.37 0.41 1.03 0.46 0.53 0.024 0.43 0.69 4.81 3.76 1.29 1.58 nd 0.28 0.37 0.46 0.35 0.21 * Sam ple nomenclature. Sam ple 1-1 denotes the sam ple w as collected 1 d a y after the spill (June 9, 2000) at sam ple site 1. bTotal concentration by LC/MS/MS represents the sum m ation o i PFHxS, PFOS. and PFO A concentrations (,ug/L) . end denotes nondetectable. Instrument detection limits (S/N > 3) for LC/M S/M S are 4 and 1 pg for P F O S and PFOA, respectively. d ncdenotes not collected. # From airport property. The total mass of PFOS that flowed through sample site 5 was estimated using PFOS surface water concentrations determined by LC/MS/MS and Etobicoke Creek flow rate data, where the flow rate was measured approximately every 15 min throughout the month of June. It was assumed that the flow rate between the sampling station and sample site 5 was equivalent. An important assumption for the total mass calculation was that the concentration between sampling 0.10 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 Upstream Concentrations O PtrfluonwctmnoB'e 5 10 15 20 Sampling Tim e (days) 25 Sam pling Tim e (days) FIGURE 3. (a) Time course of PFOA concentration in surtaci water by LC/MS/MS at ample sits 1 with increasing time (days) from original spill and time course of perfluerinsted compound con centration in surface water by LC/MS/MS at sample site 4 with increasing time (days) from original spill (b) summation of PFOS and PFHxS and (c) PFOA. dates remained the same. As an example, between the time period of sample 3-5 (June 11, 2000) and sample 6-5 (June 14,2000), the concentration of PFOS in Etobicoke Creek was assumed to be equal to the concentration measured in sample 3 -5 . Because a surface water sample was not collected the day after the spill at sample site 5, an assumption was made to equate the PFOS concentration o f sample 1-5 (not collected) to the PFOS concentration of the surface water sample collected the second day at sample site 6 (sample 2-6). With these assumptions, the total mass of PFOS that passed through sample site 5 en route to Lake Ontario from June 9 to June 29, 2000, was calculated to be 289 kg. This VOL. x*. NO. X X . xxxx / ENVIRON. SCI. & TECHNOL. E r TABLE 5. Total Psriinrinated Surfactant Concentration Determined ky " F NMR and LC/MS/MS in Surface Water Samples from an AFFF Spill distana total concn (ug/l) bv downstmm -------------------------- ampi 10a from airport (km) sample dale 1,F NMR* LC/MS/MS* sample 1-1 sample 1-2 sample 1-3 sample 1-4 sample 1-6 sample 2-1 sample 2-2 sample 2*3 sample 2*4 sample 2-5 sample 2*6 sample 3-1 sample 3-2 sample 3-3 sample 3-4 sample 3-5 sample 3-6 -3.9 4.1 6.6 8.2 15 -3.9 4.1 6.6 8.2 9.7 15 -3.9 4.1 6.6 8.2 9.7 15 June 9, 2000 June 9, 2000 June 9,2000 June 9, 2000 June 9,2000 June 10, 2000 June 10, 2000 June 10, 2000 June 10, 2000 June 10, 2000 June 10, 2000 June 11. 2000 June 11, 2000 June 11, 2000 June 11, 2000 June 11, 2000 June 11,2000 ndd 3820 4900 6000 nd nd 311 417 539 900 17000 nd nd 931 267 709 nd 0.022 815 1090 1130 0.20 0.011 93.5 114 133 185 2270 0.028 1.92 205 69.3 64.2 nd* Sample nomenclature. Sample 1-1 denotes the sample was collected 1 day after the spill (June 9. 2000) at sam ple site 1. a Total concentration (wg/U by !,F N M R represents the concentration determ ined from the C F3 chem ical shift, ~ - 7 9 ppm. ` Total concentration by LC/MS/MS represents the sum m ation of PFHxS, PFOS, and PFOA concentrations b*g/U. d nd denotes nondetectable. The :,F N M R detec tion limit is 10 /rg/L for a 100 m L a q u e o u s sam ple. * n d denotes nondetectable. Instrum ent detection limits IS/N 3) for LC/M S/M S are 4 and 1 pg for P FO S and PFOA, respectively. calculation Is reasonable given the estimated quantities (110330 kg) that entered Etobicoke Creek based on M SD S information and original spill volume (J5, 22). Etobicoke Creek Surface Water Sam ple Analysis by 19F NMR. In addition to analysis by LC/MS/MS, the surface water samples collected from Etobicoke Creek were analyzed by l9F NM R. Total perfluorinatcd surfactant concentrations ranged from nd (<10/rg/L) to 17000^g/L (Table 5). Because surface water samples collected 6 days after the spill did not contain any quantifiable perfluorinated surfactants using this method, no further analysis was performed by l9F NMR. Although there were discrepancies between the total perfluorinated surfactant concentrations determined by the two independent methods, the changes in total perfluorinated surfactant concentration trends were similar. Observed discrepancies may be attributed to the presence of other surfactants in the surface water samples that would give a 19F N M R spectrum similar to that o f PFOS and PFOA, such as an amphoteric fluorinated surfactant with a C F j group contributing to the l9F NM R spectra (32). PFOS Bioaccumulation Factor. To calculate a bioaccu mulation factor (BAF) range for PFOS in fish liver tissue, we utilized the environmental data collected from Etobicoke Creek, including the average surface water PFOS concentra tion from the 153 day sampling point (0.32 ftg/L) and the PFOS concentration in fish liver tissue collected downstream o f the airport in January 2001 (downstream 1, 39.9/rg/g) and the lowest PFOS concentration detected in fish liver tissue (airport 2,2.00 ftg/g). The latter sample concentrations were selected for calculating a field-based BAF to minim ize effects of the initial spill. Thus, we assumed the fish were in equilibrium with the creek water 7 months after the spill. The BAF range for PFOS in fish liver tissue was calculated to be approximately6300-125000. The lack of quantifiable creek water concentrations for the higher chain perfluorocarboxylates precluded the calculation of BAFs. Currently, there are no bioconcentration factors (BCFs) or BAFs published in the open literature to allow comparison for perfluoroalkanesulfonates and perfluorocarboxylates. F ENVIRON. SCI. & TECHNOL. I VOL. xx, NO. xx, xxxx 100 FIGURE 4. PFHxS, PFOS, and PFOA distribution in fish liver tissue, surface water, and an AFFF commercial product. However, preliminary laboratory BCF measurements (with rainbow trout) for a suite of perfluorocarboxylates indicate that PFOA and PFDoAhave BCFs of 8 and30000, respectively, whereas biomagnification factors were not statistically greater than 1 for any homologue (33). One explanation for the high PFOS BAFs observed in Etobicoke Creek fish liver tissue may be that the fish accumulated high molecular weight PFOSbased derivatives that are subsequently metabolized to PFOS and, therefore, bias the field BAF calculations. Unfortunately, PFOS-based derivatives that potentially could be present in Etobicoke Creek were not investigated for this study. Manufacturer data indicate that large quantities of PFOS equivalents are discharged to the aquatic environment through supply chain and consumer waste streams (35). Com parison to Other Perfluorinated Surfactant Envi ronm ental Measurem ents. The observation of perfluoro alkanesulfonates and perfluorocarboxylates in fish liver tissue and surface water samples contaminated with AFFF material is consistent with previous analyses o f AFFF concentrates and reports o f AFFF-contaminated groundwater {14, 21) (Figure 4). The concentrations o f PFOS in fish liver tissues from Etobicoke Creek were significantly higher than other published fish liver tissue PFOS concentrations (6). For example, PFOS concentrations in lake whitefish liver tissues (n = 5) ranged from 0.033 to 0.081 figtg, those in brown trout liver tissues (n = 10) ranged from 0.017 to 0.026 ftglg, and blue-fin tissue (n = 8) concentrations ranged from 0.0021 to 0.0087 fig ! g (6). The highest PFOS concentration measured in fish liver tissue collected from Etobicoke Creek (72.90fig! g) is ~1000 times greater than other reported PFOS m ea surements in fish liver tissues and is more than likely attributed to the release of high concentrations of AFFF materials into Etobicoke Creek. Similarly, the PFOS con centrations measured in Etobicoke Creek surface water immediately following the AFFF spill (i.e., 2210 y/g/L) were higher than the reported PFOS concentrations for a limited number o f samples (28-114 ng/L) in the United States (29). Im plications for Toxicity and Biodegradation. The perfluorocarboxylates (PFPeA to PFTA) measured in fish liver tissues sampled from Etobicoke Creek are of interest because perfluorinated carboxylic acids, particularly PFOA and PFDA, are known peroxisome proliferators at concentrations ranging from 50 to 350 ftM (36); PFDA was found to be a potent peroxisome proliferator in rodent liver (37). It was reported that perfluorinated carboxylic acids inhibit gap junction intercellular communication (GJIC), which was dependent on the chain length of the fluorinated tail, with PFDA inhibiting G JIC more than PFOA (36, 38). Clearly, further research is needed to assess the risk posed to aquatic organisms from the discharge of AFFF, and other perfluorinated materials, including PFOS. It is unlikely that the perfluorocarbon chain o f perfluorinated surfactants biodegrade, and this lack o f biodeg radation for perfluorinated surfactants, including PFOS and PFOA, gives rise to issues relating to the bioaccum ulation of these com pounds in the environment. Previously published work (9, 12, 39) indicated that the perfluorocarbon chain was not biodegradable, and any alteration was lim ited to nonfluorinated portions of the m olecule. Additionally, the persistence o f perfluorinated surfactants is consistent with A FFF produ ct labeling ( J5). In summary, PFOS was the predom inant perfluorinated surfactant detected In the fish liver tissue and surface water sam ples. Q uantifiable levels o f perfluoroalkanesulfonates and perfluorocarboxylates were measured in fish liver tissue and surface water collected 7 m onths an d 153 days, respectively, after the fire-fighting foam spill. Furthermore, fish and surface water samples collected upstream of the airport contained m easurable but m uch lower concentrations o f these two classes o f anionic perfluorinated surfactants. Future studies are aim ed at determining alternative sources for perfluori nated surfactants in biota and surface water. Ackaowledgineiits W e gratefully acknowledge theTrent UniversityW ater Quality Centre (Peterborough, O N , Canada) for use o f their mass spectrometry facility. W e also acknowledge Ken Com eliss (Ministry o f Natural Resources) and M ike Benner (Environ m ent Canada) for assistance with fish sam ple collection. We thank Beth W illiston and the Toronto Regional Conservation Authority for Etobicoke Creek watershed inform ation. We acknowledge Natural Resources Canada for contributions to Figure 1 and Dale Bacon and the 3M Co. for the donation of perfluorinated standards. We also gratefully acknowledge D avid Ellis (University of Toronto, Toronto, O N , Canada) for assistance with 19F N M R . We appreciate the n um erous and helpful com m ents o f the anonym ous reviewers. This work was funded in part by the Toxic Substances Research Initiative (TSRI), a research program m anaged jointly by Health Canada and Environment Canada. Literatim Cited (1) Weber, J. Business Week 2000, 96-98. (2) Brown, D.; Mayer, C. E. In Washington Post, Washington, DC, 2000; p A01. (3) Tullo, A. Chem. Eng. News 2000, May 22, 9-10. (4) Tulio, A. Chem. Eng. News 2000, M ay 28, 12-13. (5) Olsen, G. W.; Burris, J. M.; Mandel, J. H.; Zobel, L R.} . Occup. Environ. Med. 1999, 41, 799-806. (6) Giesy, J. P.; Kannan, K. 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SCI. & TECHNOL Q 7 ES&T BRIEF FOR MSC: es011001+ ISSUE: 002 Monitoring Perfluorinated Surfactants in Biota and Surface Water Samples Following an Accidental Release of Fire-Fighting Foam into Etobicoke Creek Cheryl A. Moody,* Jonathan W. Martin,* Wai Chi Kwan,* Derek C. G. Muir,4 and Scott A. Mabury*'* Perfluorooctanesulfonate and other perfluorinated surfactants were quantified in fish and surface water sampled from Etobicoke Creek following a fire-fighting foam spill. 8