Application of a comprehensive extraction technique for the determination of poly- and perfluoroalkyl substances (PFASs) in Great Lakes Region sediments.

A comprehensive method to extract perfluoroalkane sulfonic acids (PFSAs), perfluoroalkyl carboxylic acids (PFCAs), polyfluoroalkyl phosphoric acid diesters (diPAPs), perfluoroalkyl phosphinic acids (PFPiAs) and perfluoroalkyl phosphonic acids (PFPAs) from sediment and analysis by liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed and applied to sediment cores from three small isolated lakes (Plastic Lake, Lake 442, Lake Tettegouche) and Lake Ontario in the Great Lakes Region. Recoveries of the target compounds using the optimized acetonitrile/sodium hydroxide extraction ranged from 73% to 120%. The greatest concentrations of per- and polyfluorinated alkyl substances (PFASs) were recorded in sediment from Lake Ontario (ΣPFASs 13.1 ng/g), where perfluorooctane sulfonic acid (PFOS) contributed over 80% of the total. Concentrations in Lake Ontario were approximately 1-2 orders of magnitude greater than the more remote lakes subject to primarily atmospheric inputs. Whilst the PFAS contribution in Lake Ontario was dominated by PFOS, the more remote lakes contained sediment with higher proportions of PFCAs. Trace amounts of emerging PFASs (diPAPs and PFPiAs) were found in very recent surface Lake Ontario and remote lake sediments.

Fate, distribution, and contrasting temporal trends of perfluoroalkyl substances (PFASs) in Lake Ontario, Canada.

Lake Ontario water and sediment collected from tributary, nearshore, and open lake sites were analyzed for perfluoroalkyl substances (PFASs), namely perfluoroalkyl carboxylic acids (PFCAs, F(CF(2))(n)CO(2)(-); n=6-11,13) and perfluoroalkane sulfonic acids (PFSAs, F(CF(2))(n)SO(3)(-); n=6,8,10). Survey results of surface sediment and water indicated that shorter chained PFASs were predominant in and near urban/industrial area watersheds, while longer chained PFASs were predominant in fine-grained sediment from major depositional basins. Niagara River suspended solids (1981-2006) demonstrated temporal trends that may have been influenced by recent changes in North American production and use of PFASs. Perfluorooctane sulfonate (PFOS) reached a peak concentration in 2001 of 1.1 ng/g, followed by a decrease from 2001 to 2006 (half-life=9 years). Perfluorooctanoic acid (PFOA) increased from 2001 to 2006 (doubling time= 2 years) reaching a peak concentration of 0.80 ng/g. In contrast, three sediment cores from western, central, and eastern Lake Ontario showed increasing temporal trends to surface sediment for all PFASs. PFOA and PFOS concentrations increased from 1988 to 2004 (doubling time= ~ 4 years) in the western Lake Ontario core. The observed variations in temporal trends from different environmental compartments may be a result of the physico-chemical properties of PFASs, ongoing emissions, and the environmental transformation and degradation of PFAS precursor compounds.

Long-term environmental fate of perfluorinated compounds after accidental release at Toronto airport.

Perfluorooctane sulfonate (PFOS; a perfluorinated compound or PFC), its salts, and perfluorooctane sulfonyl fluoride have recently been listed in Annex B of the Stockholm Convention due to their widespread presence, persistence, and toxicity. Because of the persistent nature of PFCs, it is generally presumed that the impact of direct discharges of these chemicals on a receiving environment would be long-lasting. However, long-term environmental fate studies based on field measurements are rare. We examined spatial and long-term (9 year) temporal trends of PFCs in water, sediment, fish, and fish liver collected in 2003, 2006, and 2009 from 10 locations spanning ∼20 km in Etobicoke and Spring Creeks, where an accidental release of fire fighting foam containing PFOS from nearby Toronto International Airport occurred in 2000. Even a decade after the spill, sediment PFOS concentrations are still elevated in Spring Creek Pond which received the foam discharge; however, the major impact is relatively localized likely due to the stormwater management nature of the pond and the diluting effect of Etobicoke Creek. Fish and fish liver PFOS concentrations at a Spring Creek location downstream of Spring Creek Pond declined by about 70 and 85%, respectively, between 2003 and 2009. PFOS in water at locations further downstream in Etobicoke Creek have declined by >99.99% since the spill; however, the 2009 water and fish levels were ∼2-10 times higher than upstream locations likely due to the long-term impact of the spill as well as urbanization. The decrease in the upstream PFOS concentrations likely reflects the reduction of PFOS sources due to phased out production by 3M and regulations on the use of PFOS in fire fighting foams. Field-based sediment/water distribution coefficients (K(D)) and bioaccumulation factors (BAF) were calculated from environmental measurements. Log K(D) values were 0.54-1.65 for perfluoroalkyl sulfonates (PFASs) and 1.00-1.85 for perfluorocarboxylates (PFCAs). Log BAF(fish) ranged from 1.85 to 3.24 for PFASs and 0.88-3.47 for PFCAs, whereas log BAF(fish liver) ranged from 2.1-4.3 for PFASs and 1.0-5.0 for PFCAs.

Development of liquid chromatography atmospheric pressure chemical ionization tandem mass spectrometry for analysis of halogenated flame retardants in wastewater.

Until recently, atmospheric pressure photoionization (APPI) has typically been used for the determination of non-polar halogenated flame retardants (HFRs) by liquid chromatography (LC) tandem mass spectrometry. In this study, we demonstrated the feasibility of utilizing liquid chromatography atmospheric pressure chemical ionization (APCI) tandem mass spectrometry (LC-APCI-MS/MS) for analysis of 38 HFRs. This developed method offered three advantages: simplicity, rapidity, and high sensitivity. Compared with APPI, APCI does not require a UV lamp and a dopant reagent to assist atmospheric pressure ionization. All the isomers and the isobaric compounds were well resolved within 14-min LC separation time. Excellent instrument detection limits (6.1 pg on average with 2.0 muL injection) were observed. The APCI mechanism was also investigated. The method developed has been applied to the screening of wastewater samples for screening purpose, with concentrations determined by LC-APCI-MS/MS agreeing with data obtained via gas chromatography high resolution mass spectrometry.

Perfluoroalkyl contaminants in window film: indoor/outdoor, urban/rural, and winter/summer contamination and assessment of carpet as a possible source.

Window film concentrations of ionic perfluoroalkyl contaminants (PFCs) were determined indoors and outdoors at urban, suburban, and rural sites in or near Toronto, Ontario, Canada, to identify locations of relatively elevated concentrations and the nature of potential sources. The role of carpet installation and floor wax application as possible sources was also evaluated by sampling indoor window films at five sites before and after new carpet installations, at one site before and after a floor wax application, and at two carpet stores. Low concentrations were found in all outdoor window films, with comparable relative proportions of individual PFCs among sites, suggesting similar sources to the outdoor environment and rapid air mixing. PFCs in indoor window film were up to 20-fold greater than outdoor, providing some evidence that a significant proportion of PFCs originate from the indoor environment, although precipitation wash-off of outdoor window film may be confounding these results. For both indoor and outdoor film, PFC concentrations generally changed between the summer and winter but the chemical profiles were similar between seasons. Concentrations of PFCs in window films increased one month post carpet installation at three of the five sites, suggesting that some of the carpets may have been a source to the indoor environment. Indoor window films from two carpet stores (sigmaPFC = 16 and 7 pg/cm2) contained higher concentrations than the other indoor locations (sigmaPFC = < MDL to 4.3 pg/cm2), which may reflect the carpets stored within these buildings. The use of window film allowed collection of a wide range of samples and the results can be used to focus the efforts of more traditional air sampling campaigns.

Observation of a commercial fluorinated material, the polyfluoroalkyl phosphoric acid diesters, in human sera, wastewater treatment plant sludge, and paper fibers.

Sources of human exposure to perfluorinated carboxylic acids (PFCAs) are not well-characterized. Polyfluoroalkyl phosphoric acids (PAPs) are fluorinated surfactants used in human food contact paper products. PAPs can migrate into food and food simulants, and their bioavailability and biotransformation into PFCAs has been demonstrated using a rat model. To characterize human exposure to PAP materials, we analyzed pooled human sera samples collected in 2004 and 2005 (n = 10) and 2008 (n = 10) from the midwestern United States for the 4:2 through 10:2 PAP diesters (diPAPs). The 2004 and 2005 sera samples contained 4.5 microg/L total diPAPs, with the 6:2 diPAP dominating the congener profile at 1.9 +/- 0.4 microg/L DiPAP concentrations observed in the 2004 and 2005 human sera samples were similar to those of the C8 to C11 PFCAs (0.13 +/- 0.01 to 4.2 +/- 0.3 microg/L) monitored in the same samples. 6:2 diPAP was also consistently observed in the 2008 human sera samples at a mean concentration of 0.63 +/- 0.13 microg/L As diPAPs have been shown to degrade to PFCAs in vivo, our observation of diPAPs in human sera may be a direct connection between the legacy of human PFCA contamination and PAPs commercial applications. Wastewater treatment plant (WWTP) sludge and paper fibers were analyzed for diPAPs as a proxy for human use and potential exposure to diPAPs. DiPAPs were observed in WWTP sludge at concentrations ranging from 47 +/- 22 to 200 +/- 130 ng/g, a range similar to perfluorooctane sulfonic acid (PFOS) (100 +/- 70 ng/g) and greater than the C8 to C11 PFCAs (1.6 +/- 0.6 to 0.17 +/- 0.10 ng/g) observed in the same samples. DiPAPs were observed in paper fiber extracts at concentrations ranging from 34 +/- 30 to 2200 +/- 400 ng/g. The high diPAP concentrations in WWTP sludge suggest PAP materials may be prevalent in our daily lives.

Perfluorinated phosphonic acids in Canadian surface waters and wastewater treatment plant effluent: discovery of a new class of perfluorinated acids.

The environmental prevalence of a new class of perfluorinated acids, the perfluorinated phosphonic acids (PFPAs), was determined in Canadian surface waters and wastewater treatment plant (WWTP) effluent. For quality control and comparison, the C8- to C11-perfluorinated carboxylic acids and perfluorooctane sulfonic acid were included in the analysis. Water samples were extracted using weak anion-exchange solid-phase extraction cartridges. Perfluorinated phosphonic acids were observed in 80% of surface water samples and in six of the seven WWTP effluent samples. The C8-PFPA was observed at concentrations ranging from 88 +/- 33 to 3400 +/- 900 pg/L in surface waters and from 760 +/- 270 to 2500 +/- 320 pg/L in WWTP effluent. To our knowledge, this is the first observation of PFPAs in the environment. Given their structural similarities with perfluorinated carboxylic and sulfonic acids, PFPAs are expected to be persistent. The observation of PFPAs in the majority of samples analyzed here suggests they are prevalent environmental contaminants and should be considered in future environmental monitoring campaigns to better understand the total burden of fluorinated materials in the environment.

Factors influencing trends of polychlorinated naphthalenes and other dioxin-like compounds in lake trout (Salvelinus namaycush) from Lake Ontario, North America (1979-2004).

Concentrations of polychlorinated naphthalenes (PCNs) were determined in archived lake trout (Salvelinus namaycush) from Lake Ontario, North America, collected between 1979 and 2004 to evaluate their temporal trends and the factors influencing their trends. Concentrations of PCNs, as well as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and non- and mono-ortho-substituted polychlorinated biphenyls (DL-PCBs), which were measured for comparative purposes, declined by eight-, seven-, and fivefold, respectively, between 1979 and 2004. Apparent elimination rate constants (k2) were calculated as the slopes of the regression lines of concentration versus time for PCN, DL-PCB, and PCDD/F congeners to compare the rate of decrease among congeners within and between compound classes. The k2 values for PCNs that had two pairs or three adjacent carbons unsubstituted with chlorine (congeners that can be biotransformed by vertebrates) were not significantly different from zero, indicating no decline in fish. For PCN congeners having no adjacent carbons unsubstituted with chlorine, the k2 values generally increased with hydrophobicity and degree of chlorination. This pattern differed from that of PCDD/Fs and DL-PCBs and from previous findings for non-DL-PCBs, for which the rate of contaminant decline decreased with hydrophobicity, and the pattern also differed from expectations based on thermodynamics. Differences in the rate of decline of PCN congeners may be caused by changes in source or mixture formulations over time and/or metabolic dechlorination of the less stable, higher-chlorinated PCNs 73, 74, and 75 to lower-chlorinated congeners. Based on suggested dioxin toxic equivalency factors, PCN concentrations in these whole lake trout may be sufficient to trigger consumption restrictions in Ontario, Canada, and our results suggest that PCNs merit incorporation into monitoring and assessment programs.

Temporal trends of perfluoroalkyl compounds with isomer analysis in lake trout from Lake Ontario (1979-2004).

The temporal trends of perfluoroalkyl compounds (PFCs), including C7-C15 perfluorocarboxylates (PFCAs), perfluorosulfonates (PFSAs) and heptadecafluorooctane sulfonamide (PFOSA), were determined in lake trout collected between 1979 and 2004 from Lake Ontario. The average concentrations of total PFSAs (+/- standard error of the mean; range) increased from 20 ng g(-1) wet weight (+/- 4; 8-26) in 1979, peaked at 70 ng g(-1) (+/- 7; 58-91) in 1993, and were 46 ng g(-1) (+/- 10; 30-83) in 2004, with perfluorooctane sulfonate (PFOS) asthe most abundant PFC. The PFCAs exhibited similar temporal variation, with concentrations increasing from 1.4 ng g(-1) (+/- 0.1; 0.9-1.9) in 1979 to 9.4 ng g(1) (+/- 3.1; 3-17) in 1988, and were 6.8 ng g(-1) (+/- 1.0; 4.5-9.8) in 2004. Individual mean PFCA concentrations varied between 0.2 and 2 ng g(-1) (wet weight). Perfluorodecane sulfonate (PFDS) and PFOSA were the only compounds showing a declining trend in the past decade, after reaching a peak value in 1993. Branched C11 and C13 PFCA isomers were detected in the lake trout and confirmed in Niagara River suspended sediments, with trends in both matrices suggesting that declining emissions or use of products containing these isomers in part account for the observed PFCA trends in the mid-1990s. However, the most recent samples, comprised almost exclusively of linear isomers, indicate that current PFCA sources to Lake Ontario result from the telomerization process of linear telogens.

Trace level determination of perfluorinated compounds in water by direct injection.

A new, fast LC-MS/MS method for the determination of perfluorinated surfactants in water samples by direct injection without pre-concentration is reported. The current method requires only 4 min to analyze nine perfluoroalkyl compounds in a single analytical run. Standard addition and internal standard quantification were used to determine the level of some perfluorinated carboxylic and sulfonic acids, including perfluorooctanoic sulfonate (PFOS) and perfluorooctanoic acid (PFOA), in Great Lakes water samples. Statistically significant differences were observed between the results obtained using different quantification methods. A relatively small difference between the PFOS values obtained with the standard addition method, with and without peak area normalization, clearly indicates that standard addition is the best quantification method when mass-labeled standards are not available. Based on the paired t-test statistical analysis, the concentrations calculated using external standardization were the least accurate, with the highest mean difference from the standard addition calculated values. Both PFOS and PFOA were present at less than 10 ng l(-1) in all Great Lake samples. Higher levels were detected in tributaries of Lake Ontario and effluents from sewage treatment plants.

Spatial distribution of perfluoroalkyl contaminants in lake trout from the Great Lakes.

Individual whole body homogenates of 4 year old lake trout (Salvelinus namaycush) samples collected in 2001 from each of the Great Lakes were extracted using a novel fluorophilicity cleanup step and analyzed for perfluoroalkyl compounds (PFCs). Standard addition and internal standardization were used for quantification. Results were reported (+/- SE) for perfluorinated carboxylates (PFCAs), perfluorinated sulfonates (PFSAs), and unsaturated fluorotelomer carboxylates (8:2 and 10:2 FTUCA). The lowest average concentration of sigmaPFC was found in samples from Lake Superior (13+/-1 ng g(-1)), while the highest average concentration was found in samples from Lake Erie (152+/-14 ng g(-1)). Samples from Lake Ontario (60+/-5 ng g(-1)) and Lake Huron (58 +/-10 ng g(-1)) showed similar average sigmaPFC concentrations, although the perfluorinated sulfonate/carboxylate ratios were different. The major perfluoroalkyl contaminant observed was perfluorooctane sulfonate (PFOS) with the highest concentration found in samples from Lake Erie (121+/-14 ng g(-1)), followed by samples from Lake Ontario (46+/-5 ng g(-1)), Lake Huron (39 +/-10 ng g(-1)), Lake Michigan (16+/-3 ng g(-1)), and Lake Superior (5+/-1 ng g(-1)). Perfluorodecane sulfonate (PFDS) was detected in 89% of the samples, with the highest concentration in Lake Erie samples (9.8+/-1.6 ng g(-1)), and lowest concentration in samples from Lake Superior (0.7 +/- 0.1 ng g(-1)). Statistically significant correlations were observed between PFOS and PFDS concentrations, and PFOS concentration and body weight, respectively. The PFCAs were detected in all samples, with the highest total average concentration in samples from Lake Erie (19 ng g(-1)), followed by samples from Lake Huron (16 ng g(-1)), Lake Ontario (10 ng g(-1)), Lake Michigan (9 ng g(-1)) and Lake Superior (7 ng g(-1)). The compounds with significant contributions to the sigmaPFCA concentrations were PFOA and C9-C13-PFCAs. The 8:2 FTUCA was detected at concentrations ranging between 0.1 and 0.2 ng g-1, with the highest level in samples showing also elevated concentrations of PFOA (4.4 ng g(-1) for Lake Michigan vs 1.5 ng g(-1) for all other samples). The 10:2 FTUCA was detected only in 9% of all samples (nd, 45 pg g(-1)). For those PFCs where we determined lake water concentrations, the highest log BAFs were calculated for PFOS (4.1), PFDA (3.9), and PFOSA (3.8).

Distribution and transportability of hexabromocyclododecane (HBCD) in the Asia-Pacific region using skipjack tuna as a bioindicator.

The geographical distribution of hexabromocyclododecane (HBCD) was investigated through analysis of muscle tissue of skipjack tuna (Katsuwonus pelamis) collected from offshore waters of Asia-Pacific region (Japan, Taiwan, Philippines, Indonesia, Seychelles, Brazil, Japan Sea, East China Sea, South China Sea, Indian Ocean and North Pacific Ocean). HBCD was detected in almost all samples analyzed (<0.1 to 45 ng/g lipid weight basis), indicating widespread presence of this compound in the marine environment. Elevated concentrations of HBCD were found in skipjack tuna from areas around Japan, which have the larger modern industrial/urban societies, and implicated these areas as primary regional sources. All three individual HBCD isomers (alpha-, gamma- and beta-HBCD) were detected in almost all samples; the percentage contribution of the alpha-isomer to total HBCD increased with increasing latitude. The estimated empirical 1/2 distance for alpha-HBCD was 8500 km, which is one of the highest atmospheric transportability among various halogenated persistent organic pollutants (POPs).