Search

Only a few dozens of the several thousand existing per- and polyfluoroalkyl substances (PFAS) are monitored using conventional target analysis. This study employed suspect screening to examine patterns of emerging and novel PFAS in German and Chinese river water affected by industrial point sources. In total, 86 PFAS were (tentatively) identified and grouped into 18 structure categories. Homologue patterns revealed distinct differences between fluoropolymer production sites of the two countries. In the Chinese Xiaoqing River Basin, the C 8 homologue was the most prevalent compound of the emerging series of chlorinated perfluoroalkyl carboxylic acids (Cl-PFCAs) and perfluoroalkylether carboxylic acids (PFECAs). In contrast, C 6 and shorter homologues were dominant in the German Alz River. This indicates that the phaseout of long-chain compounds in Europe and their ongoing production in Asian countries also apply to unregulated emerging PFAS classes. Additional characteristics to differentiate the point sources were the peak area ratio of perfluorobutane sulfonic acid (PFBS) versus the emerging compound hydro-substituted PFBS (H-PFBS) as well as the occurrence of byproducts of the sulfonated tetrafluoroethylene-based polymer Nafion. The large number of identified unregulated PFAS underlines the importance of a grouping approach on a regulatory level, whereas the revealed contamination patterns can be used to estimate, prioritize, and minimize contributions of specific sources.

Pesticides are widespread anthropogenic chemicals and well-known environmental contaminants of concern. Much less is known about transformation products (TPs) of pesticides and their presence in the environment. We developed a novel suspect screening approach for not well-explored pesticides ( n = 16) and pesticide TPs ( n = 242) by integrating knowledge from national monitoring with high-resolution mass spectrometry data. Weekly time-integrated samples were collected in two Swedish agricultural streams using the novel Time-Integrating, MicroFlow, In-line Extraction (TIMFIE) sampler. The integration of national monitoring data in the screening approach increased the number of prioritized compounds approximately twofold (from 23 to 42). Ultimately, 11 pesticide TPs were confirmed by reference standards and 12 TPs were considered tentatively identified with varying levels of confidence. Semiquantification of the newly confirmed TPs indicated higher concentrations than their corresponding parent pesticides in some cases, which highlights concerns related to (unknown) pesticide TPs in the environment. Some TPs were present in the environment without co-occurrence of their corresponding parent compounds, indicating higher persistency or mobility of the identified TPs. This study showcased the benefits of integrating monitoring knowledge in this type of studies, with advantages for suspect screening performance and the possibility to increase relevance of future monitoring programs.

Emergent aquatic insects are important food subsidies to riparian food webs but can also transfer waterborne contaminants to the terrestrial environment. This study aimed to quantitatively assess this biodriven transfer for per- and polyfluoroalkyl substances (PFAS). Aquatic insect larvae, emergent aquatic insects, terrestrial consumers, sediment, and water were collected from a contaminated lake and stream and an uncontaminated pond, and analyzed for PFAS and stable isotopes of carbon and nitrogen. Top predators in this study were spiders, which showed the highest average ∑ 24 PFAS concentration of 1400 ± 80 ng g -1 dry weight (dw) at the lake and 630 ng g -1 dw at the stream. The transfer of PFAS from the lake to the riparian zone, via deposition of emergent aquatic insects, was 280 ng ∑ 24 PFAS m -2 d -1 in 2017 and only 23 ng ∑ 24 PFAS m -2 d -1 in 2018. Because of higher production of emergent aquatic insects, the lake had higher PFAS transfer and higher concentrations in terrestrial consumers compared to the stream, despite the stream having higher PFAS concentration in water and aquatic insect larvae. Our results indicate that biodriven transfer of PFAS from the aquatic systems and subsequent uptake in terrestrial food webs depend more on emergence amounts, i.e., aquatic prey availability, rather than on PFAS concentrations in water and aquatic prey.

An improved quantitative and qualitative understanding of the interaction of per- and polyfluoroalkyl substances (PFASs) and short-range ordered Fe (hydr)oxides is crucial for environmental risk assessment in environments low in natural organic matter. Here, we present data on the pH-dependent sorption behavior of 12 PFASs onto ferrihydrite. The nature of the binding mechanisms was investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and by phosphate competition experiments. Sulfur K-edge XANES spectroscopy showed that the sulfur atom of the head group of the sulfonated PFASs retained an oxidation state of +V after adsorption. Furthermore, the XANES spectra did not indicate any involvement of inner-sphere surface complexes in the sorption process. Adsorption was inversely related to pH ( p < 0.05) for all PFASs (i.e., C 3 -C 5 and C 7 -C 9 perfluorocarboxylates, C 4 , C 6 , and C 8 perfluorosulfonates, perfluorooctane sulfonamide, and 6:2 and 8:2 fluorotelomer sulfonates). This was attributed to the pH-dependent charge of the ferrihydrite surface, as reflected in the decrease of surface ζ-potential with increasing pH. The importance of surface charge for PFAS adsorption was further corroborated by the observation that the adsorption of PFASs decreased upon phosphate adsorption in a way that was consistent with the decrease in ferrihydrite ζ-potential. The results show that ferrihydrite can be an important sorbent for PFASs with six or more perfluorinated carbons in acid environments (pH ≤ 5), particularly when phosphate and other competitors are present in relatively low concentrations.

A retrospective analysis of a comprehensive series of high-volume air samples ( n = 70) collected during 2010-2011 in Toronto (Canada) was performed. Seven UV compounds were analyzed by gas chromatography-tandem mass spectrometry (GC-MS/MS) with sum of concentrations (gas + particle phase) ranging from 80 to 2030 pg/m 3 . Homosalate (HMS) was the most prevalent organic UV-filter in air (47% of the total concentration), followed by 2-ethylhexyl salicylate (EHS, ∼29%), E- and Z-2-ethylhexyl 4-methoxycinnamate (EHMC, ∼17%). Ambient air (gas + particle phase) concentrations of organic UV-filters showed a strong seasonality, with peak levels during the summer. An analysis of Clausius-Clapeyron slopes indicated that much of the ambient burden of organic UV-filters are explained by volatilization from terrestrial and aquatic surfaces and supplemented with human activities and use of lotions and sunscreens, containing organic UV-filters, in addition to its use in plastics, textiles, paints, and pesticides. The results showed that organic UV-filters exist mainly in the gas phase with some exceptions, for instance, octocrylene (OCR), which was associated with both gas and particle phases, and avobenzone (AVB), which was predominantly in the particle phase. Lastly, this study revealed the need for basic physical chemical property data for organic UV-filters, including information on transformation rates and products, for better evaluating their environmental fate and effects.

The occurrence of per- and polyfluoroalkyl substances (PFASs) in aquatic ecosystems is a global concern because of their persistence, potential bioaccumulation, and toxicity. In this study, we investigated a PFAS-contaminated pond in Sweden to assess the cross-boundary transfer of PFASs from the aquatic environment to the riparian zone via emergent aquatic insects. Aquatic and terrestrial invertebrates, surface water, sediments, soils, and plants were analyzed for 24 PFASs including branched isomers. Stable isotope analysis of carbon and nitrogen was performed to elucidate the importance of diet and trophic position for PFAS uptake. We present the first evidence that PFASs can propagate to the riparian food web via aquatic emergent insects. Elevated Σ 24 PFAS concentrations were found in aquatic insect larvae, such as dragon- and damselflies, ranging from 1100 to 4600 ng g -1 dry weight (dw), and remained high in emerged adults (120-3500 ng g -1 dw), indicating exposure risks for top predators that prey in riparian zones. In terrestrial invertebrate consumers, PFAS concentrations increased with the degree of aquatic-based diet and at higher trophic levels. Furthermore, stable isotope data together with calculated bioaccumulation factors indicated that bioconcentration of PFASs was the major pathway of exposure in the aquatic food web and bioaccumulation in the riparian food web.

We investigated associations between serum perfluoroalkyl acid (PFAA) concentrations in children aged 4, 8, and 12 years (sampled in 2008-2015; n = 57, 55, and 119, respectively) and exposure via placental transfer, breastfeeding, and ingestion of PFAA-contaminated drinking water. Sampling took place in Uppsala County, Sweden, where the drinking water has been historically contaminated with perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHxS), perfluorooctanesulfonate (PFOS), perfluoroheptanoate (PFHpA), and perfluorooctanoate (PFOA). PFOS showed the highest median concentrations in serum (3.8-5.3 ng g -1 serum), followed by PFHxS (1.6-5.0 ng g -1 serum), PFOA (2.0-2.5 ng g -1 serum), and perfluorononanoate (PFNA) (0.59-0.69 ng g -1 serum) in children. Including all children, serum PFOA, PFHxS, and PFOS concentrations in children increased 10, 10, and 1.3% (adjusted mean), respectively, per unit (ng g -1 serum) of increase in the maternal serum level (at delivery), the associations being strongest for 4 year-old children. PFHxS and PFOS significantly increased 3.9 and 3.8%, respectively, per month of nursing, with the highest increase for 4 year-olds. PFOA, PFBS, PFHxS, and PFOS increased 1.2, 207, 7.4, and 0.93%, respectively, per month of cumulative drinking water exposure. Early life exposure to PFOA, PFHxS, and PFOS is an important determinant of serum concentrations in children, with the strongest influence on younger ages. Drinking water with low to moderate PFBS, PFHxS, PFOS, and PFOA contamination is an important source of exposure for children with background exposure from other sources.

This study demonstrates that regulatory databases combined with the latest advances in high resolution mass spectrometry (HRMS) can be efficiently used to prioritize and identify new, potentially hazardous pollutants being discharged into the aquatic environment. Of the approximately 23000 chemicals registered in the database of the National Swedish Product Register, 160 potential organic micropollutants were prioritized through quantitative knowledge of market availability, quantity used, extent of use on the market, and predicted compartment-specific environmental exposure during usage. Advanced liquid chromatography (LC)-HRMS-based suspect screening strategies were used to search for the selected compounds in 24 h composite samples collected from the effluent of three major wastewater treatment plants (WWTPs) in Sweden. In total, 36 tentative identifications were successfully achieved, mostly for substances not previously considered by environmental scientists. Of these substances, 23 were further confirmed with reference standards, showing the efficiency of combining a systematic prioritization strategy based on a regulatory database and a suspect-screening approach. These findings show that close collaboration between scientists and regulatory authorities is a promising way forward for enhancing identification rates of emerging pollutants and expanding knowledge on the occurrence of potentially hazardous substances in the environment.

Little is known about factors influencing infant perfluorinated alkyl acid (PFAA) concentrations. Associations between serum PFAA concentrations in 2-4-month-old infants ( n = 101) and determinants were investigated by multiple linear regression and general linear model analysis. In exclusively breast-fed infants, maternal serum PFAA concentrations 3 weeks after delivery explained 13% (perfluoroundecanoic acid, PFUnDA) to 73% (perfluorohexanesulfonate, PFHxS) of infant PFAA concentration variation. Median infant/maternal ratios decreased with increasing PFAA carbon chain length from 2.8 for perfluoroheptanoic acid and perfluorooctanoic acid (PFOA) to 0.53 for PFUnDA and from 1.2 to 0.69 for PFHxS and perfluorooctanesulfonate (PFOS). Infant PFOA, perfluorononanoic acid (PFNA), and PFOS levels increased 0.7-1.2% per day of gestational age. Bottle-fed infants had mean concentrations of PFAAs 2 times lower than and a mean percentage of branched (%br) PFOS isomers 1.3 times higher than those of exclusively breast-fed infants. PFOA, PFNA, and PFHxS levels increased 8-11% per week of exclusive breast-feeding. Infants living in an area receiving PFAA-contaminated drinking water had 3-fold higher mean perfluorobutanesulfonate (PFBS) and PFHxS concentrations and higher mean %br PFHxS. Prenatal PFAA exposure and postnatal PFAA exposure significantly contribute to infant PFAA serum concentrations, depending on PFAA carbon chain length. Moderately PFBS- and PFHxS-contaminated drinking water is an important indirect exposure source.

Concentrations of polycyclic aromatic compounds (PACs), including 19 polycyclic aromatic hydrocarbons (PAHs) and 15 PAH-derivatives (oxygenated and nitrogen heterocyclic PAHs), were measured in streams in a remote headwater catchment in northern Europe and in more urbanized, downstream areas. Sampling was conducted during 2014 to 2016 and included the main hydrological seasons (snow-free, snow-covered, and spring flood) at six sampling sites. Levels of the targeted PACs varied substantially over time and space and were up to 110-fold (on average 17-fold) and 7000-fold (on average 670-fold) higher for PAHs and PAH-derivatives, respectively, during spring flood compared with preceding snow-covered and snow-free seasons. Higher levels of ∑PACs were generally found in a headwater stream draining a mire than at an adjacent forested site, with up to 20 times and 150 times higher levels for ∑PAH and ∑PAH-derivatives, respectively. The particle-bound PAC levels were positively correlated to surface runoff in the mire stream (∑PAHs: p = 0.032; ∑PAH-derivatives: p = 0.040) but not in the corresponding forest stream, during snowmelt and winter base flow. In more urbanized downstream areas, particle-bound PACs were instead strongly associated with suspended particulate matter ( p < 0.05; ∑PAHs and ∑PAH-derivatives except one site). Levels of ∑PACs in the streamwater were on average 3-fold higher downstream of the most densely populated area than at the outlet of the headwater catchment. The higher PAC levels in the downstream water compared to the remote headwater were clearer when normalized to SPM amounts (instead of water volume), with a gradual downstream trend between the sites.

The aim of this study was to assess per- and polyfluoroalkyl substances (PFASs) in the Swedish aquatic environment, identify emission sources, and compare measured concentrations with environmental quality standards (EQS) and (drinking) water guideline values. In total, 493 samples were analyzed in 2015 for 26 PFASs (∑ 26 PFASs) in surface water, groundwater, landfill leachate, sewage treatment plant effluents and reference lakes, focusing on hot spots and drinking water sources. Highest ∑ 26 PFAS concentrations were detected in surface water (13 000 ng L -1 ) and groundwater (6400 ng L -1 ). The dominating fraction of PFASs in surface water were perfluoroalkyl carboxylates (PFCAs; 64% of ∑ 26 PFASs), with high contributions from C 4 -C 8 PFCAs (94% of ∑PFCAs), indicating high mobility of shorter chain PFCAs. In inland surface water, the annual average (AA)-EQS of the EU Water Framework Directive of 0.65 ng L -1 for ∑PFOS (linear and branched isomers) was exceeded in 46% of the samples. The drinking water guideline value of 90 ng L -1 for ∑ 11 PFASs recommended by the Swedish EPA was exceeded in 3% of the water samples from drinking water sources ( n = 169). The branched isomers had a noticeable fraction in surface- and groundwater for perfluorooctanesulfonamide, perfluorohexanesulfonate, and perfluorooctanesulfonate, highlighting the need to include branched isomers in future guidelines.

Fire training facilities and other areas suffer from serious per- and polyfluoroalkyl substance (PFAS) contamination in soil, surface water, and groundwater due to regular practices with PFAS-containing aqueous firefighting foams (AFFFs). Therefore, the uptake of 26 PFASs in plants and the contamination of soil and groundwater has been investigated at a fire training site at Stockholm Arlanda airport, Stockholm (Sweden) in 2016. Elevated ∑ 26 PFAS levels were detected in soil and groundwater ranging from 16 to 160 ng g -1 dry weight (dw) and 1200-34 000 ng L -1 , respectively. Samples from different plant species and tissues (i.e., roots, trunk/cores, twigs, leaves/needles) of the local plant community were taken, namely silver birch (Betula pendula), Norway spruce (Picea abies), bird cherry (Prunus padus), mountain ash (Sorbus aucuparia), ground elder (Aegopodium podagraria), long beechfern (Phegopteris connectilis), and wild strawberry (Fragaria vesca). The plants showed a high variability of concentrations with highest ∑ 26 PFAS concentrations in vegetative compartments with up to 97 ng g -1 wet weight (ww) and 94 ng g -1 ww in birch leaves and spruce needles, respectively. Annual ground cover plants such as long beechfern and ground elder, and bushes like bird cherry showed concentrations up to 6.9, 23, and 21 ng g -1 ww, respectively. The bioconcentration factors (BCFs; plant/soil ratios) were highest in foliage, while the total tree burden of ∑ 26 PFASs per tree was up to 11 mg for birch and 1.8 mg for spruce. Considering a shelterwood system with mixed stands of silver birch and spruce in combination with regular harvest of leaves and birch sap and an understory of ground elder, it is potentially feasible to remove 1.4 g of ∑ 26 PFASs per year and hectare from (heavily) contaminated sites. An alternative approach is the coppicing of birch trees in combination with an understory of ground elder, potentially removing 0.65 g yr -1 ha -1 of ∑ 26 PFASs, while a simple meadow with ground elder can remove 0.55 g yr -1 ha -1 ∑ 26 PFASs.

We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.

A passive air sampling network has been established to investigate polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at Global Atmospheric Passive Sampling (GAPS) sites and six additional sites in the Group of Latin American and Caribbean Countries (GRULAC) region. The air sampling network covers background, agricultural, rural, and urban sites. Samples have been collected over four consecutive periods of 6 months, which started in January 2011 [period 1 (January to June 2011), period 2 (July to December 2011), period 3 (January to June 2012), and period 4 (July 2012 to January 2013)]. Results show that (i) the GAPS passive samplers (PUF disk type) and analytical methodology are adequate for measuring PCDD/F burdens in air and (ii) PCDD/F concentrations in air across the GRULAC region are widely variable by almost 2 orders of magnitude. The highest concentrations in air of Σ4-8PCDD/Fs were found at the urban site São Luis (Brazil, UR) (i.e., 2560 fg/m3) followed by the sites in São Paulo (Brazil, UR), Mendoza (Argentina, RU), and Sonora (Mexico, AG) with values of 1690, 1660, and 1610 fg/m3, respectively. Very low concentrations of PCDD/Fs in air were observed at the background site Tapanti (Costa Rica, BA), 10.8 fg/m3. This variability is attributed to differences in site characteristics and potential local/regional sources as well as meteorological influences. The measurements of PCDD/Fs in air agree well with model-predicted concentrations performed using the Global EMEP Multimedia Modeling System (GLEMOS) and emission scenario constructed on the basis of the UNEP Stockholm Convention inventory of dioxin and furan emissions.

Cyclic and linear volatile methylsiloxanes (cVMSs and lVMSs, respectively) were measured in ambient air over a period of over one year in Toronto, Canada. Air samples were collected using passive air samplers (PAS) consisting of sorbent-impregnated polyurethane foam (SIP) disks in parallel with high volume active air samplers (HV-AAS). The average difference between the SIP-PAS derived concentrations in air for the individual VMSs and those measured using HV-AAS was within a factor of 2. The air concentrations (HV-AAS) ranged 22-351 ng m(-3) and 1.3-15 ng m(-3) for ΣcVMSs (D3, D4, D5, D6) and ΣlVMSs (L3, L4, L5), respectively, with decamethylcyclopentasiloxane (D5) as the dominant compound (∼75% of the ΣVMSs). Air masses arriving from north to northwest (i.e., less populated areas) were significantly less contaminated with VMSs compared to air arriving from the south that are impacted by major urban and industrial areas in Canada and the U.S. (p < 0.05). In addition, air concentrations of ΣcVMSs were lower during major snowfall events (on average, 73 ng m(-3)) in comparison to the other sampling periods (121 ng m(-3)). Ambient temperature had a small influence on the seasonal trend of VMS concentrations in air, except for dodecamethylcyclohexasiloxane (D6), which was positively correlated with the ambient temperature (p < 0.001).

Two passive air sampler (PAS) media were characterized under field conditions for the measurement of per- and polyfluoroalkyl substances (PFASs) in the atmosphere. The PASs, consisting of polyurethane foam (PUF) and sorbent-impregnated PUF (SIP) disks, were deployed for over one year in parallel with high volume active air samplers (HV-AAS) and low volume active air samplers (LV-AAS). Samples were analyzed for perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer methacrylates (FTMACs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs). Sampling rates and the passive sampler medium (PSM)-air partition coefficient (KPSM-A) were calculated for individual PFASs. Sampling rates were similar for PFASs present in the gas phase and particle phase, and the linear sampling rate of 4 m(-3) d(-1) is recommended for calculating effective air sample volumes in the SIP-PAS and PUF-PAS for PFASs except for the FOSAs and FOSEs in the PUF-PAS. SIP disks showed very good performance for all tested PFASs while PUF disks were suitable only for the PFSAs and their precursors. Experiments evaluating the suitability of different isotopically labeled fluorinated depuration compounds (DCs) revealed that (13)C8-perfluorooctanoic acid (PFOA) was suitable for the calculation of site-specific sampling rates. Ambient temperature was the dominant factor influencing the seasonal trend of PFASs.

Gas-phase perfluoroalkyl carboxylic acids (PFCAs) sorb strongly on filter material (i.e., GFF, QFF) used in conventional high volume air samplers, which results in an overestimation of the particle-phase concentration. In this study, we investigated an improved technique for measuring the gas-particle partitioning of per- and polyfluoroalkyl substances (PFASs) using an annular diffusion denuder sampler. Samples were analyzed for 7 PFAS classes [i.e., PFCAs, perfluoroalkane sulfonic acids (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer methacrylates (FTMACs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs)]. The measured particulate associated fraction (Φ') using the diffusion denuder sampler generally followed the trend FTACs (0%) < FTOHs (~8%) < FOSAs (~21%) < PFSAs (~29%) < FOSEs (~66%), whereas the Φ' of the C(8)-C(18) PFCAs increased with carbon chain length, and ranged from 6% to 100%. The ionizability of some PFASs, when associated with particles, is an important consideration when calculating the gas-particle partitioning coefficient as both ionic and neutral forms can be present in the particles. Here we differentiate between a gas-particle partitioning coefficient for neutral species, K(p), and one that accounts for both ionic and neutral species of a compound, K(p)'. The measured K(p)' for PFSAs and PFCAs was 4-5 log units higher compared to the interpolated K(p) for the neutral form only. The measured K(p)' can be corrected (to apply to the neutral form only) with knowledge of the pK(a) of the chemical and the pH of the condensed medium ("wet" particle or aqueous aerosol). The denuder-based sampling of PFASs has yielded a robust data set that demonstrates the importance of atmospheric pH and chemical pK(a) values in determining gas-particle partitioning of PFASs.

Perfluoroalkyl compounds (PFCs) were determined in 22 surface water samples (39-76°N) and three sea ice core and snow samples (77-87°N) collected from North Pacific to the Arctic Ocean during the fourth Chinese Arctic Expedition in 2010. Geographically, the average concentration of ∑PFC in surface water samples were 560 ± 170 pg L(-1) for the Northwest Pacific Ocean, 500 ± 170 pg L(-1) for the Arctic Ocean, and 340 ± 130 pg L(-1) for the Bering Sea, respectively. The perfluoroalkyl carboxylates (PFCAs) were the dominant PFC class in the water samples, however, the spatial pattern of PFCs varied. The C(5), C(7) and C(8) PFCAs (i.e., perfluoropentanoate (PFPA), perfluoroheptanoate (PFHpA), and perfluorooctanoate (PFOA)) were the dominant PFCs in the Northwest Pacific Ocean while in the Bering Sea the PFPA dominated. The changing in the pattern and concentrations in Pacific Ocean indicate that the PFCs in surface water were influenced by sources from the East-Asian (such as Japan and China) and North American coast, and dilution effect during their transport to the Arctic. The presence of PFCs in the snow and ice core samples indicates an atmospheric deposition of PFCs in the Arctic. The elevated PFC concentration in the Arctic Ocean shows that the ice melting had an impact on the PFC levels and distribution. In addition, the C(4) and C(5) PFCAs (i.e., perfluorobutanoate (PFBA), PFPA) became the dominant PFCs in the Arctic Ocean indicating that PFBA is a marker for sea ice melting as the source of exposure.

The extent to which different manufacturing sources and long-range transport pathways contribute to perfluorooctanoate (PFOA) in the world's oceans, particularly in remote locations, is widely debated. Here, the relative contribution of historic (i.e., electrochemically fluorinated) and contemporary (i.e., telomer) manufacturing sources was assessed for PFOA in various seawater samples by an established isomer profiling technique. The ratios of individual branched PFOA isomers were indistinguishable from those in authentic historic standards in 93% of the samples examined, indicating that marine processes had little influence on isomer profiles, and that isomer profiling is a valid source apportionment tool for seawater. Eastern Atlantic PFOA was largely (83-98%) of historic origin, but this decreased to only 33% close to the Eastern U.S. seaboard. Similarly, PFOA in the Norwegian Sea was near exclusively historic, but the relative contribution decreased to ∼50% near the Baltic Sea. Such observations of contemporary PFOA in coastal source regions coincided with elevated concentrations, suggesting that the continued production and use of PFOA is currently adding to the marine burden of this contaminant. In the Arctic, a spatial trend was observed whereby PFOA in seawater originating from the Atlantic was predominantly historic (up to 99%), whereas water in the Archipelago (i.e., from the Pacific) was predominantly of contemporary origin (as little as 17% historic). These data help to explain reported temporal and spatial trends from Arctic wildlife biomonitoring, and suggest that the dominant PFOA source(s) to the Pacific and Canadian Arctic Archipelago are either (a) from direct emissions of contemporary PFOA via manufacturing or use in Asia, or (b) from atmospheric transport and oxidation of contemporary PFOA-precursors.

Polyfluoroalkyl compounds (PFCs) were determined in air around a wastewater treatment plant (WWTP) and two landfill sites using sorbent-impregnated polyurethane foam (SIP) disk passive air samplers in summer 2009. The samples were analyzed for five PFC classes (i.e., fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamides (FOSAs), sulfonamidoethanols (FOSEs), perfluoroalkyl sulfonic acids (PFSAs), and perfluoroalkyl carboxylic acids (PFCAs)) to investigate their concentration in air, composition and emissions to the atmosphere. ∑PFC concentrations in air were 3-15 times higher within the WWTP (2280-24 040 pg/m(3)) and 5-30 times higher at the landfill sites (2780-26 430 pg/m(3)) compared to the reference sites (597-1600 pg/m3). Variations in the PFC pattern were observed between the WWTP and landfill sites and even within the WWTP site. For example, FTOHs were the predominant PFC class in air for all WWTP and landfill sites, with 6:2 FTOH as the dominant compound at the WWTP (895-12 290 pg/m(3)) and 8:2 FTOH dominating at the landfill sites (1290-17 380 pg/m(3)). Furthermore, perfluorooctane sulfonic acid (PFOS) was dominant within the WWTP (43-171 pg/m(3)), followed by perfluorobutanoic acid (PFBA) (55-116 pg/m(3)), while PFBA was dominant at the landfill sites (101-102 pg/m(3)). It is also noteworthy that the PFCA concentrations decreased with increasing chain length and that the emissions for the even chain length PFCAs outweighed emissions for the odd chain length compounds. Furthermore, highly elevated PFC concentrations were found near the aeration tanks compared to the other tanks (i.e., primary and secondary clarifier) and likely associated with increased volatilization during aeration that may be further enhanced through aqueous aerosol-mediated transport. ∑PFC yearly emissions estimated using a simplified dispersion model were 2560 g/year for the WWTP, 99 g/year for landfill site 1, and 1000 g/year for landfill site 2. These results highlight the important role of WWTPs and landfills as emission sources of PFCs to the atmosphere.

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in tawny owl (Strix aluco) eggs collected in Central Norway over a period of 24 years (1986-2009). Concentrations of 12 PFCs, including C(6)-C(8), C(10) perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfonamide (PFOSA), and C(8)-C(14) perfluoroalkyl carboxylates (PFCAs), were measured, whereas saturated and unsaturated fluorotelomer carboxylates and shorter chain PFSAs and PFCAs were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (geometric mean 10.1 ng/g wet weight (ww)), followed by perfluorotridecanoate (PFTriDA) (0.36 ng/g ww) and perfluoroundecanoate (PFUnDA) (0.19 ng/g ww). Significant decreasing concentrations were found for PFOS with an annual decrease of 1.6% (1986-2009), while, conversely, the C(10)-C(13) PFCA concentrations increase significantly with an annual increase of 4.2-12% (1986-2009). Consequently, the contribution of PFOS to the ∑PFCs decreased, whereas the contribution of the ∑PFCAs increased over the time. Toxicological implications for tawny owls are limited, but the maximal PFOS concentration found in this stu0dy is about 20 times lower than the predicted avian no effect concentration (PNEC) which suggest adverse effects caused by PFOS are unlikely. However, tawny owls are exposed to a mixture of various PFCs, and PFCA concentrations still increase.

The relationships between climate variability, feeding conditions, and the annual accumulation of polychlorinated biphenyls (PCB), 1,1-dichloro-2,2-bis (p-chlorophenyl) ethylene (p,p'-DDE) and polybrominated diphenyl ethers (PBDE) in eggs (n = 168) of tawny owls (Strix aluco) were assessed over a 24-year period (1986-2009) in Central Norway. Winter climate variables included the North Atlantic Oscillation (NAO) and snow conditions, whereas feeding conditions were assessed using vole abundance. The concentrations of all compounds declined between 79% (p,p'-DDE) and 86% (PBDE) over the time period. For PCB and p,p'-DDE, the accumulation was positively associated with snow depth, and negatively associated with NAO (i.e., high accumulation in cold and dry winters) when vole abundance was low, suggesting trade-offs between winter severity and feeding conditions. That is, females mobilize more body fat reserves in cold winters when feeding conditions are poor, which results in increased circulating contaminant concentrations and maternal transfer to the eggs. Owls may also have been forced to feed on prey with higher contaminant loads due to restricted prey availability. For the recently banned PBDEs, the accumulation was high when NAO was low, while snow depth was positively associated with PBDE accumulation only when feeding conditions were good. This suggests somewhat different dynamics of PBDE in the environment or in the owls, compared to PCB and p,p'-DDE. However, climate and feeding conditions explained as much of the annual variation in concentrations of all POPs, as the overall decreasing trend over the 24 years. Hence, such factors should be considered in monitoring programs for POPs. Moreover, to better understand the mechanisms of climate effects on POP accumulation, future studies should measure pollutants in different components of the food chain.

Seawater and air samples were collected aboard the FS Polarstern during the cruises ANT-XXV/1 + 2 in the Atlantic and Southern Ocean in 2008. The particulate and dissolved phase in water and particulate and gaseous phase in air were analyzed separately for nine polybrominated diphenyl ethers (PBDEs) and six non-PBDE brominated flame retardants (BFRs). Air concentrations of 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and hexabromobenzene (HBB) in the gaseous and particulate phase (median = 0.56 pg m(-3) for DPTE and 0.92 pg m(-3) for HBB) were comparable to ∑(9)PBDEs (1.0 pg m(-3)). Pentabromotoluene (PBT) was detectable in ∼30% of the gaseous phase samples, whereas concentration of 2,4,6-tribromophenyl allylether (ATE), hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) and 2-ethyl-1-hexyl 2,3,4,5-tetrabromobenzoate (EHTBB) were below their method detection limits. DPTE, and PBDEs were also found in seawater at low pg per liter levels. Elevated seawater concentrations of PBDEs and DPTE were measured in the English Channel and close to South African coast. Concentrations of DPTE, BDE-47, and BDE-99 in the atmosphere generally decreased from Europe toward the Southern Ocean, whereas no latitudinal trend was observed in seawater. Air-water exchange gradients suggested net deposition dominates for all selected substances. The medians of net deposition fluxes for the air-water gas exchange were 83, 21, 69, 20, and 781 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB, whereas medians of dry deposition fluxes were 2.0, 0.3, 1.2, 1.0, and 0.5 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB. Overall, these results highlight the important role of the long-range atmospheric transport of PBDE and non-PBDE BFRs to remote regions.

Sorbent-impregnated polyurethane foam (SIP) disk passive air samplers were deployed alongside polyurethane foam (PUF) disk samplers at 20 sites during the 2009 spring sampling period of the Global Atmospheric Passive Sampling (GAPS) Network. The SIP disk samplers consisted of PUF disks impregnated with finely ground XAD-4 resin. The addition of XAD-4 greatly improves the sorptive capacity of the PUF disk samplers for more volatile and polar chemicals, and allows for linear-phase sampling over several weeks for these compounds. The SIP and PUF disks were analyzed for polychlorinated biphenyls (PCBs), neutral polyfluoroalkyl compounds (PFCs), and ionic PFCs. Correlations between sampler-derived air concentrations for PCBs in the PUF and SIP disks samplers were significant (p < 0.05). The SIP disks effectively captured 4-50% more of the low molecular weight PCBs than the PUF disks samplers, and the PUF disks also had limitations for time-weighted passive sampling of neutral PFCs in air. Theoretical uptake curves for PUF disks showed rapid equilibration occurring in just hours for 8:2 FTOH and in a few days for MeFOSE, while theoretical curves for SIP disks showed superior sampling profiles for the neutral PFCs. PFCs were measured on SIP disks at all sites with 8:2 FTOH being the dominant compound detected and urban centers (n = 3) having the highest total neutral PFC concentrations ranging from 51.7 to 248 pg/m(3). A positive correlation was found between the FTOHs and FOSAs/FOSEs (p < 0.001, Pearson correlation) indicating similar contamination sources. The SIP disk appears to be a promising passive air sampler for measuring both emerging and legacy POPs on a global scale. They can also be used as a complement to the PUF disk sampler for capturing broader classes of compounds, or as a replacement for PUF disks entirely, especially when longer than quarterly deployment periods are desired.

The partitioning behavior of per- and polyfluoroalkyl compounds (PFCs) between pore water and sediment in two sediment cores collected from Tokyo Bay, Japan, was investigated. In addition, the fluxes and temporal trends in one dated sediment core were studied. Short-chain perfluoroalkyl carboxylic acids (PFCAs) (C < or = 7) were found exclusively in pore water, while long-chain PFCAs (C > or = 11) were found only in sediment The perfluoroalkyl sulfonates (PFSAs), n-ethylperfluoro-1-octanesulfonamidoacetic acid (N-EtFOSAA), and perfluorooctane sulfonamide (PFOSA) seemed to bind more strongly to sediment than PFCAs. The enrichment of PFCs on sediment increased with increasing organic matter and decreasing pH. The perfluorocarbon chain length and functional group were identified as the dominating parameters that had an influence on the partitioning behavior of the PFCs in sediment The maximum SigmaPFC contamination in sediment was observed in 2001-2002 to be a flux of 197 pg cm(-2) yr(-1). Statistically significant increased concentrations in Tokyo Bay were found for perfluorooctanesulfonate (PFOS) (1956-2008), perfluorononanoic acid (PFNA) (1990-2008), and perfluoroundecanoic acid (PFUnDA) (1990-2008). Concentrations of PFOSA and N-EtFOSAA increased between 1985 and 2001, but after 2001, the concentration decreased significantly, which corresponded with the phase out of perfluorooctyl sulfonyl fluoride-based compounds by the 3M Company in 2000.

Perfluoroalkyl compounds (PFCs) were determined in 2 L surface water samples collected in the Atlantic Ocean onboard the research vessels Maria S. Merian along the longitudinal gradient from Las Palmas (Spain) to St. Johns (Canada) (15 degrees W to 52 degrees W) and Polarstern along the latitudinal gradient from the Bay of Biscay to the South Atlantic Ocean (46 degrees N to 26 degrees S) in spring and fall 2007, respectively. After filtration the dissolved and particulate phases were extracted separately, and PFC concentrationswere determined using high-performance liquid chromatography interfaced to tandem mass spectrometry. No PFCs were detected in the particulate phase. This study provides the first concentration data of perfluorooctanesulfonamide (FOSA), perfluorohexanoic acid, and perfluoroheptanoic acid from the Atlantic Ocean. Results indicate that trans-Atlantic Ocean currents caused the decreasing concentration gradient from the Bay of Biscay to the South Atlantic Ocean and the concentration drop-off close to the Labrador Sea. Maximum concentrations were found for FOSA, perfluorooctanesulfonate, and perfluorooctanoic acid at 302, 291, and 229 pg L(-1), respectively. However, the concentration of each single compound was usually in the tens of picograms per liter range. South of the equator only FOSA and below 4 degrees S no PFCs could be detected.

Neutral, volatile polyfluorinated alkyl substances (PFAS) were measured in environmental air samples at two different sites in Northern Germany in spring 2005. The sampling locations were chosen to cover a metropolitan and a rural site, the Hamburg city center, and Waldhof, a background monitoring site. An optimized and validated analytical protocol was used to analyze two sets of parallel high-volume air samples. For both sampling locations as well as for individual samples, field blanks were taken to monitor possible background contamination. Gas chromatography coupled to mass spectrometry using positive chemical ionization (GC/ PCI-MS) was used for quantitative analyses. This article describes the first air concentration data of volatile PFAS outside North America reported in the peer-reviewed literature. The wide distribution of fluorotelomer alcohols (FTOHs), fluorinated sulfonamides, and sulfonamidoethanols (FOSAs/FOSEs) in German environmental air is presented. Furthermore, two volatile PFAS, i.e., N-methyl fluorooctane sulfonamide (NMeFOSA) and 4:2 FTOH, were determined for the first time in environmental air. Minimum-maximum sigmaFTOH concentrations of 64-311 pg/m3 (remote) up to 150-546 pg/m3 (urban) and minimum-maximum sigmaFOSA + FOSE concentrations between 12 and 54 pg/m3 (remote) and 29 and 151 pg/m3 (urban) were determined. 8:2 FTOH and 6:2 FTOH were found to be the predominant POPs determined in Waldhof so far. Blank contamination was found to be negligible. A significant correlation was found with the ambient temperature for the partitioning of airborne FOSEs between the gaseous and particulate phase (R = 0.853), whereas FTOHs and FOSAs were almost exclusively found in the gaseous phase. Furthermore, highest airborne PFAS concentrations were determined at relatively high ambient temperatures. Correlation coefficients (R) for sigmaFTOH and sigmaFOSA + FOSE concentrations with temperature were 0.954 and 0.968, respectively. Finally, the PFAS concentrations determined in this study are set into context with levels of "classical" persistent organic pollutants (POPs) in the same region and PFAS data available for North America.