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Polyfluoroalkyl and perfluoroalkyl substances (PFASs) are distributed ubiquitously in the aquatic environment, which raises concern for the flora and fauna in hydrosystems. The present critical review focuses on the fate and adverse effects of PFASs in the aquatic environment. The PFASs are continuously emitted into the environment from point and nonpoint sources such as sewage treatment plants and atmospheric deposition, respectively. Although concentrations of single substances may be too low to cause adverse effects, their mixtures can be of significant environmental concern. The production of C8 -based PFASs (i.e., perfluorooctane sulfonate [PFOS] and perfluorooctanoate [PFOA]) is largely phased out; however, the emissions of other PFASs, in particular short-chain PFASs and PFAS precursors, are increasing. The PFAS precursors can finally degrade to persistent degradation products, which are, in particular, perfluoroalkane sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs). In the environment, PFSAs and PFCAs are subject to partitioning processes, whereby short-chain PFSAs and PFCAs are mainly distributed in the water phase, whereas long-chain PFSAs and PFCAs tend to bind to particles and have a substantial bioaccumulation potential. However, there are fundamental knowledge gaps about the interactive toxicity of PFAS precursors and their persistent degradation products but also interactions with other natural and anthropogenic stressors. Moreover, because of the continuous emission of PFASs, further information about their ecotoxicological potential among multiple generations, species interactions, and mixture toxicity seems fundamental to reliably assess the risks for PFASs to affect ecosystem structure and function in the aquatic environment., (© 2014 SETAC.)

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).

Per- and polyfluoroalkyl substances (PFAS) were measured systematically in a snowpack in northern Sweden to determine chemical behaviour during seasonal melt. Average PFAS concentrations were generally low, but displayed a wide range with median (range) concentrations of PFOA and PFOS of 66.5 pg L(-1) (ND-122) and 20.5 pg L(-1) (2.60-253) respectively. Average concentrations of the shorter chain, C4 and C5 perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs), were ∼10-fold higher. Differences in the PFAS concentrations and profile were observed between surface snow and deeper layers, with evidence of PFAS migration to deeper snow layers as melt progressed. Chemical loads (ng m(-2)) for C4-9 PFCAs decreased gradually as melt progressed, but increased for C4, C6-8 PFSAs and the longer chain C10-12 PFCAs. This enrichment in the diminishing snowpack is an unusual phenomenon that will affect PFAS elution with meltwater and subsequent entry to catchment surface waters., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

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.

Concentrations of neutral poly- and perfluoroalkyl substances (PFASs), such as fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sufonamidoethanols (FASEs), and fluorotelomer acrylates (FTACs), have been simultaneously determined in surface seawater and the atmosphere of the North Sea. Seawater and air samples were taken aboard the German research vessel Heincke on the cruise 303 from 15 to 24 May 2009. The concentrations of FTOHs, FASAs, FASEs, and FTACs in the dissolved phase were 2.6-74, <0.1-19, <0.1-63, and <1.0-9.0 pg L(-1), respectively. The highest concentrations were determined in the estuary of the Weser and Elbe rivers and a decreasing concentration profile appeared with increasing distance from the coast toward the central part of the North Sea. Gaseous FTOHs, FASAs, FASEs, and FTACs were in the range of 36-126, 3.1-26, 3.7-19, and 0.8-5.6 pg m(-3), which were consistent with the concentrations determined in 2007 in the North Sea, and approximately five times lower than those reported for an urban area of Northern Germany. These results suggested continuous continental emissions of neutral PFASs followed by transport toward the marine environment. Air-seawater gas exchanges of neutral PFASs were estimated using fugacity ratios and the two-film resistance model based upon paired air-seawater concentrations and estimated Henry's law constant values. Volatilization dominated for all neutral PFASs in the North Sea. The air-seawater gas exchange fluxes were in the range of 2.5×10(3)-3.6×10(5) pg m(-2) for FTOHs, 1.8×10(2)-1.0×10(5) pg m(-2) for FASAs, 1.1×10(2)-3.0×10(5) pg m(-2) for FASEs and 6.3×10(2)-2.0×10(4) pg m(-2) for FTACs, respectively. These results suggest that the air-seawater gas exchange is an important process that intervenes in the transport and fate for neutral PFASs in the marine environment.

Patient satisfaction is viewed as a significant indicator of quality of care. More specifically, improving patient satisfaction related to communication about medications and potential side effects can improve healthcare outcomes. Patient satisfaction scores related to medication side effects on a neuro-medical surgical unit were monitored following a quality improvement program. These patients frequently experience cognitive impairment and functional difficulties that can affect the way they understand and handle medications. The purpose of this quality improvement practice change was to (a) develop an educational approach for post acute neurosurgical patients and (b) evaluate whether the use of the approach is successful in improving patient satisfaction scores related to medication education on side effects. The quality improvement program interventions included (a) patient informational handouts inserted into admission folders, (b) nurse education about the importance of providing education on side effects to patient and discussion of their involvement with the program, (c) unit flyers with nurse education, and (d) various communications with bedside nurses through personal work mail and emails. The primary focus was for nurses to employ the "teach back" method to review and reinforce the medication side-effect teaching with patients. Evaluation of the data showed an increase in patient satisfaction after the implementation of the "Always Ask" program.

In Canada, perfluoroalkyl acids (PFAAs) have been the focus of several monitoring programs and research and surveillance studies. Here, we integrate recent data and perform a multi-media assessment to examine the current status and ongoing trends of PFAAs in Canada. Concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain perfluorocarboxylates (PFCAs) in air, water, sediment, fish, and birds across Canada are generally related to urbanization, with elevated concentrations observed around cities, especially in southern Ontario. PFOS levels in water, fish tissue, and bird eggs were below their respective Draft Federal Environmental Quality Guidelines, suggesting there is low potential for adverse effects to the environment/organisms examined. However, PFOS in fish and bird eggs tended to exceed guidelines for the protection of mammalian and avian consumers, suggesting a potential risk to their wildlife predators, although wildlife population health assessments are needed to determine whether negative impacts are actually occurring. Long-term temporal trends of PFOS in suspended sediment, sediment cores, Lake Trout (Salvelinus namaycush), and Herring Gull (Larus argentatus) eggs collected from Lake Ontario increased consistently from the start of data collection until the 1990s. However, after this time, the trends varied by media, with concentrations stabilizing in Lake Trout and Herring Gull eggs, and decreasing and increasing in suspended sediment and the sediment cores, respectively. For PFCAs, concentrations in suspended sediment, sediment cores, and Herring Gulls generally increased from the start of data collection until present and concentrations in Lake Trout increased until the late 1990s and subsequently stabilized. A multimedia comparison of PFAA profiles provided evidence that unexpected patterns in biota of some of the lakes were due to unique source patterns rather than internal lake processes. High concentrations of PFAAs in the leachate and air of landfill sites, in the wastewater influent/effluent, biosolids, and air at wastewater treatment plants, and in indoor air and dust highlight the waste sector and current-use products (used primarily indoors) as ongoing sources of PFAAs to the Canadian environment. The results of this study demonstrate the utility of integrating data from different media. Simultaneous evaluation of spatial and temporal trends in multiple media allows inferences that would be impossible with data on only one medium. As such, more co-ordination among monitoring sites for different media is suggested for future sampling, especially at the northern sites. We emphasize the importance of continued monitoring of multiple-media for determining future responses of environmental PFAA concentrations to voluntary and regulatory actions., (Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.)

In situ measurements of air and water phases at a wastewater treatment plant (WWTP) were used to investigate the partitioning behavior of perfluorocarboxylic acids (PFCAs), perfluorosulfonic acids (PFSAs) and perfluorooctyl sulfonamide (HFOSA) and their conjugate bases (PFC(-)s, PFS(-)s, and FOSA(-), respectively). Particle-dissolved (Rd) and air-water (QAW) concentration ratios were determined at different tanks of a WWTP. Sum of concentrations of C4-12,14 PFC(A)s, C4,6,8,10 PFS(A)s and (H)FOSA were as high as 50 pg m(-3) (atmospheric gas phase), 2300 ng L(-1) (aqueous dissolved phase) and 2500 ng L(-1) (aqueous particle phase). Particle-dissolved concentration ratios of total species, log Rd, ranged from -2.9 to 1.3 for PFS(A)s, from -1.9 to 1.1 for PFC(A)s and was 0.71 for (H)FOSA. These field-based values agree well with equilibrium partitioning data reported in the literature, suggesting that any in situ generation from precursors, if they are present in this system, occurs at a slower rate than the rate of approach to equilibrium. Acid QAW were also estimated. Good agreement between the QAW and the air-water equilibrium partition coefficient for C8PFCA suggests that the air above the WWTP tanks is at or near equilibrium with the water. Uncertainties in these QAW values are attributed mainly to variability in pKa values reported in the literature. The WWTP provides a unique environment for investigating environmental fate processes of the PFCAs and PFSAs under 'real' conditions in order to better understand and predict their fate in the environment., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Dichlorodiphenyltrichloroethanes (DDTs) are persistent organic pollutants that were widely used in China, especially eastern China, as insecticides. This work investigated the concentration, dissipation, and volatilization of DDTs and enantiomeric fractions (EFs) of o,p'-DDD and o,p'-DDT in agricultural soils collected in 2006 from 58 sites in Zhejiang province. Correlations between DDT residues and soil properties were assessed to determine the effect of soil properties on the environmental attenuation of DDTs. High concentrations and detection frequencies were found for DDTs in agricultural soils in the region even though large-scale use of DDTs was banned over 20 years ago. The amount of DDTs was about 485 tons in the upper 20 cm of the soil column of cropland in the province in 2010, with a dissipation half-life of ~9 years. The mass flux of DDTs was 43 ng m(-2) h(-1), which corresponds to emissions of 7.6 tons with an emission factor of 1.6% in 2006. The low p,p'-DDT/p,p'-DDE ratios and high o,p'-DDT/p,p'-DDT ratios suggest that there were no recent inputs of DDTs but fresh application of dicofol, which contains DDT (o,p'-DDT in particular) impurities. The significant positive correlation between concentrations of DDTs and total organic carbon content (TOC) indicates the distribution of DDTs fit a typical "secondary distribution" pattern. DEVrac of o,p'-DDD, which is defined as the absolute value of EFs subtracted from 0.5, was significantly related with most of the physicochemical and microbial soil properties. The most significant correlation is that between DEVrac of o,p'-DDD and soil pH (p < 0.001), indicating that the soil pH plays a key role in enantioselective residues of DDTs.

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.

Long-term temporal trends (1991-2008) and spatial differences of perfluoroalkylated substances (PFASs) were investigated in harbor porpoise (Phocoena phocoena) liver samples of juvenile females from the Baltic and North Sea. Additionally, spatial differences between the populations in the Baltic Sea and Atlantic Ocean (i.e. Iceland and Norway) and the influence of the body mass, age and sex on the PFAS concentrations were examined. Perfluorooctane sulfonate (PFOS) was the predominant compound with a concentration range of 160-2425 ng/g wet weight (ww), followed by perfluorooctane sulfonamide (PFOSA, 1-237 ng/g ww) and perfluoroundecanoate (PFUnA, 3-124 ng/g ww). In terms of temporal trends, perfluoroalkyl sulfonates (PFSAs) and PFOSA concentrations decreased over time, while, conversely, the C(9)-C(13) perfluoroalkyl carboxylate (PFCA) concentrations increased. Spatial distribution of the contaminant concentrations showed consistently higher concentrations in the Baltic Sea and lowest concentrations in the Icelandic population of the Atlantic Ocean., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The spatial distribution of per- and polyfluoroalkyl compounds (PFCs) were investigated in coastal waters collected onboard research vessel Snow Dragon from the East to South China Sea in 2010. All samples were prepared by solid-phase extraction and analyzed using high performance liquid chromatography/negative electrospray ionization-tandem mass spectrometry (HPLC/(-)ESI-MS/MS). Concentrations of 9 PFCs, including C(4) and C(8) (PFBS, PFOS) perfluoroalkyl sulfonate (PFSAs), C(5)-C(9) and C(13) (PFPA, PFHxA, PFHpA, PFOA, PFNA, PFTriDA) perfluoroalkyl carboxylates (PFCAs), and N-ethyl perfluorooctane sulfonamide (EtFOSA) were quantified. The ΣPFC concentrations ranged from 133 pg/L to 3320 pg/L, with PFOA (37.5-1541 pg/L), PFBS (23.0-941 pg/L) and PFHpA (0-422 pg/L) as dominant compounds. Concentrations of PFCs were greater in coastal waters along Shanghai, Ningbo, Taizhou, Xiamen and along coastal cities of the Guangdong province compared to less populated areas along the east Chinese coast. Additionally, the comparison with other seawater PFC measurements showed lower levels in this study., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

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.

Overestimation of the particle phase concentration collected on glass-fiber filters (GFFs) has been reported for perfluoroalkyl carboxylic acids (PFCAs) using conventional high volume air samplers. In this study, per- and polyfluoroalkyl substances (PFASs) were determined in the gas and particulate phases using colocated annular diffusion denuder and high volume air samplers at a semiurban site in Toronto, Canada, in winter 2010. Samples were analyzed for 7 PFAS classes (i.e., PFCAs, perfluoro-alkane sulfonic acids (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer methacrylates (FTMACs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs)). The gas diffusion coefficients for individual PFASs were calculated and the denuder performance was evaluated. Modeled subcooled liquid vapor pressures (p(L)) correlated well with the vapor phase breakthrough for the denuder and high volume air systems. Total air concentrations for PFASs measured using annular diffusion denuders and high volume samplers were in agreement within a factor of 4; however, much greater differences were observed for measurements of gas-particle partitioning. Vapor phase PFSAs and PFCAs can adsorb to the GFF using high volume air samplers, resulting in much higher particle-associated fractions for these chemicals compared to the annular diffusion denuder sampler. This effect was not observed for the FTOHs, FTMACs, FTACs, FOSAs, and FOSEs. Thus, for investigations of gas-particle partitioning of PFSAs and PFCAs, the diffusion denuder sampler is the preferred method. The results of this study improve our understanding of the gas-particle partitioning of PFASs, which is important for modeling their long-range transport in air.

Volatile methyl siloxanes (VMSs) are a class of chemicals with an increasing range of applications and widespread distribution in the environment. Passive air samplers (PAS) comprising sorbent-impregnated polyurethane-foam (SIP) disks were first calibrated and then deployed around two wastewater treatment plants (WWTPs) and at two landfill sites to investigate inputs of VMSs to air. SIP-derived air concentrations for ΣVMSs (ng/m(3)) at background sites on the perimeter of the WWTP were 479 ± 82.3 and comparable to results for the upwind samples at the landfills (333 ± 194). Order of magnitude higher concentrations of ΣVMSs (ng/m(3)) were found for on-site samples at the WWTPs (3980 ± 2620) and landfills (4670 ± 3360). Yearly emissions (kg/yr) to air were estimated and ranged from 60-2100 and 80-250, respectively, for the cyclic VMSs. These findings demonstrate and quantify for the first time, waste sector emissions of VMSs to the atmosphere., (Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.)

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.

Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (K(OC)) decreased in the following order: PFOSA (log K(OC) = 4.1 ± 0.35 cm³ g⁻¹)>PFOS (3.7 ± 0.56 cm³ g⁻¹) > PFOA (2.4 ± 0.12 cm³ g⁻¹). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C(4)-C(10) PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C(7)-C(14) PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g(-1) wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g(-1) ww). C(6)-C(8) PFSAs, PFOSi and C(7)-C(13) PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C(12) and C(13) PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C(12)-C(14)) shows that further work on the reduction of environmental emissions of PFCs are necessary., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

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.

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C(4)-C(10) PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C(7)-C(14) PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1,444 ng g(-1) wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g(-1) ww). C(6)-C(8) PFSAs, PFOSi and C(7)-C(13) PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C(12) and C(13) PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C(12)-C(14)) shows that further work on the reduction of environmental emissions of PFCs are necessary., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

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.

The occurrence and fate of polyfluoroalkyl compounds (PFCs) in the aquatic environment has been recognized as one of the emerging issues in environmental chemistry. PFCs comprise a diverse group of chemicals that are widely used as processing additives during fluoropolymer production and as surfactants in consumer applications for over 50 years. PFCs are known to be persistent, bioaccumulative and have possible adverse effects on humans and wildlife. As a result, perfluorooctane sulfonate (PFOS) has been added to the persistent organic pollutants (POPs) list of the Stockholm Convention in May 2009. However, their homologues, neutral precursor compounds and new PFCs classes continue to be produced. In general, several PFCs from different classes have been detected ubiquitously in the aqueous environment while the concentrations usually range between pg and ng per litre for individual compounds. Sources of PFCs into the aqueous environment are both point sources (e.g., wastewater treatment plant effluents) and nonpoint sources (e.g., surface runoff). The detected congener composition in environmental samples depends on their physicochemical characteristics and may provide information to their sources and transport pathways. However, the dominant transport pathways of individual PFCs to remote regions have not been conclusively characterised to date. The objective of this article is to give an overview on existing knowledge of the occurrence, fate and processes of PFCs in the aquatic environment. Finally, this article identifies knowledge gaps, presents conclusions and recommendations for future work.

The concentration profile of 40 polyfluoroalkyl substances (PFAS) in surface water along the River Rhine watershed from the Lake Constance to the North Sea was investigated. The aim of the study was to investigate the influence of point as well as diffuse sources, to estimate fluxes of PFAS into the North Sea and to identify replacement compounds of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In addition, an interlaboratory comparison of the method performance was conducted. The PFAS pattern was dominated by perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) with concentrations up to 181 ng/L and 335 ng/L, respectively, which originated from industrial point sources. Fluxes of SigmaPFAS were estimated to be approximately 6 tonnes/year which is much higher than previous estimations. Both, the River Rhine and the River Scheldt, seem to act as important sources of PFAS into the North Sea., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

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.

Polyfluoroalkyl compounds (PFCs) can be found ubiquitously in the marine environment. The transport of PFCs to remote locations is assumed to be by direct transport via oceanic water currents or indirectly via atmospheric transport of volatile precursor compounds. This study investigates the influence of ocean currents and atmospheric transport to the East Greenland Arctic Ocean (67.5-80.4 degrees N). In this study, 38 water samples were collected in the Arctic summer in 2009 and analyzed by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). Concentrations of three PFC classes could be quantified (i.e., perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl sulfonamides) predominantly in a low pg L(-1) range. Dominating compounds were PFOSA and PFOA with mean concentrations of 61 pg L(-1) and 51 pg L(-1), respectively. Statistically significant higher concentrations for PFOSA and PFHxA in the samples taken north of 75 degrees N indicate an atmospheric influence on the concentrations found in the water samples. Significant differences in concentrations of PFHxS, PFHxA, PFHpA and PFOA for samples taken in coastal areas indicate an influence from the Greenlandic mainland.

Polyfluoroalkyl compounds (PFCs) are widely used in industry and consumer products. These products could end up finally in landfills where their leachates are a potential source for PFCs into the aqueous environment. In this study, samples of untreated and treated leachate from 22 landfill sites in Germany were analysed for 43 PFCs. SigmaPFC concentrations ranged from 31 to 12,819 ng/L in untreated leachate and 4-8060 ng/L in treated leachate. The dominating compounds in untreated leachate were perfluorobutanoic acid (PFBA) (mean contribution 27%) and perfluorobutane sulfonate (PFBS) (24%). The discharge of PFCs into the aqueous environment depended on the cleaning treatment systems. Membrane treatments (reverse osmosis and nanofiltrations) and activated carbon released lower concentrations of PFCs into the environment than cleaning systems using wet air oxidation or only biological treatment. The mass flows of summation operatorPFCs into the aqueous environment ranged between 0.08 and 956 mg/day., (Copyright 2009 Elsevier Ltd. All rights reserved.)

This study examined the environmental behaviour and fate of polyfluoroalkyl compounds (PFCs) found in water, suspended particulate matter (SPM) and sediment. The sampling of the sediment was performed at two stations from Tokyo Bay, Japan, in 2008. In addition, a depth profile of seawater was collected at three water layers from both sampling stations. The summation operatorPFC concentrations ranged from 16.7 to 42.3ngL(-1) in the water column, from 6.4 to 15.1ngg(-1) dry weight (dw) in the SPM fraction and from 0.29 to 0.36dw in surface sediment. The distribution of PFCs was found to depend on their physicochemical characteristics. While short-chain perfluoroalkyl carboxylic acids (PFCAs) (C<7) were exclusively detected in the dissolved phase, longer-chain PFCAs (C7), perfluoroalkyl sulfonates (PFSAs), ethylperfluorooctane sulfonamidoacetic acid (EtFOSAA), and perfluorooctane sulfonamide (PFOSA) appeared to bind more strongly to particles. Results showed that the sorption of PFCs on SPM increases by 0.52-0.75 log units for each additional CF(2) moiety and that the sorption of PFSAs was 0.71-0.76 log units higher compared to the PFCA analogs. In addition, the sorption of PFCs was influenced by the organic carbon content. These data are essential for modelling the transport and environmental fate of PFCs., (2010 Elsevier Ltd. All rights reserved.)

The global distribution of perfluoroalkyl compounds (PFCs) were investigated in surface water samples collected onboard the Polarstern in Northern Europe, Atlantic and Southern Ocean (52 degrees N-69 degrees S) in 2008. The water samples were solid-phase extracted with Oasis WAX cartridges and analysed using the high-performance liquid chromatography interfaced to tandem mass spectrometry. Concentrations of various PFCs, including C(4), C(6), C(8) perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfinate (PFOSi), C(5)-C(12) perfluoroalkyl carboxylic acids (PFCA) and perfluorooctane sulfonamide (FOSA) were quantified. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the predominant compounds with a maximum concentration of 232 and 223pgL(-1), respectively. Results indicate that industrial areas like the European Continent act as source of PFCs, while ocean water is an important as a sink as well as the transport medium of these compounds. Interestingly, in the equator area the summation operatorPFC concentration increased, which indicates that there exists an atmospheric or other unknown input source of PFCs. In the Southern Ocean only PFOS was detected which could be caused by atmospheric transport of its precursors.

The spatial distribution of 15 polyfluoroalkyl compounds (PFCs) in surface water was investigated in the North Sea, Baltic Sea and Norwegian Sea. In addition, an interlaboratory comparison of the sampling techniques and analysis was conducted. Highest concentration in the North Sea was found near the coast, whereas the summation operatorPFC concentration decreased rapidly from 18.4 to 0.07 ng l(-1) towards the open North Sea. The river Elbe could identify as a local input source for PFCs into the North Sea, whereas perfluorobutanoic acid (PFBA) was transported into the sampling area with the easterly current. In contrast to the North Sea, the distribution of PFCs in the Baltic Sea was relatively homogenous, where diffuse sources dominated. In general, the composition profile was influenced from local sources caused by human activities, whereas atmospheric depositions of here analysed PFCs were negligible, but it could have possibly an influence on low contaminated sites like the open North Sea or Norwegian Sea., (Copyright 2009 Elsevier Ltd. All rights reserved.)

The spatial distribution of polyfluoroalkyl compounds (PFCs) was investigated in dab (Limanda limanda) bile fluids collected from Iceland and the North Sea. Concentrations of various PFCs, including perfluorinated sulfonates (C(4)-C(6), C(8) PFSAs), perfluorinated carboxylic acids (C(9)-C(14) PFCAs) and n-methyl perfluorooctane sulfonamidoethanol (MeFOSE), were quantified. Perfluorooctane sulfonate (PFOS) was the predominant compound with highest concentrations along the Danish and German coast (mean 9.36ng/g wet weight (ww)). Significantly lower PFOS concentrations were found at the other sampling stations in the North Sea and Iceland (p<0.01, t-test). Conversely, the spatial distribution of the PFCAs in Iceland and the North Sea was more uniform. The most abundant PFCA was perfluorononanoic acid (PFNA), while the mean concentration decreased with increasing chain length from 4.7 ng/g ww for PFNA to 0.04 ng/g ww for perfluorotetradecanoic acid (PFTeDA). Overall, the different spatial distribution of PFCs indicates different origin of sources and different transportation mechanism., (Copyright 2009 Elsevier Ltd. All rights reserved.)

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.

Polyfluorinated compounds (PFCs) were investigated in waste water treatment plant (WWTP) effluents and surface waters of the River Elbe from samples collected in 2007. Concentrations of various PFCs, including C(4)-C(8) perfluorinated sulfonates (PFSAs), C(6) and C(8) perfluorinated sulfinates, 6:2 fluorotelomer sulfonate, C(5)-C(13) perfluorinated carboxylic acids (PFCAs), C(4) and C(8) perfluoroalkyl sulfonamides and 6:2, 8:2 and 10:2 unsaturated fluorotelomercarboxylic acids were quantified. Sum PFC concentrations of the river water ranged from 7.6 to 26.4ngL(-1), whereas sum PFC concentrations of WWTP effluents were approximately 5-10 times higher (30.5-266.3ngL(-1)), indicating that WWTPs are potential sources of PFCs in the marine environment. PFC patterns of different WWTP effluents varied depending on the origin of the waste water, whereas the profile of PFC composition in the river water was relatively constant. In both kinds of water samples, perfluorooctanoic acid (PFOA) was the major PFC, whereas perfluorobutane sulfonate (PFBS) was the predominant PFSA.

The spatial distribution of polyfluoroalkyl compounds (PFCs) and their composition profile was investigated in 48 water samples collected from the German Bight. All samples were prepared by solid-phase extraction with Strata XAW cartridges and analysed using high performance liquid chromatography/negative electrospray ionisation-tandem mass spectrometry (HPLC/(-)ESI-MS/MS). Concentrations of various PFCs, including perfluorinated sulfonates (PFSAs), perfluorinated carboxylic acids (PFCAs), unsaturated fluorotelomercarboxylic acids, perfluoralkyl sulfonamide and sulfonamidoethanol, were quantified. The Sigma PFC concentration ranges from 9.36 ng L(-1) to 31.2 ng L(-1), while perfluorobutane sulfonate (PFBS, 3.38-17.7 ng L(-1)) and perfluorooctanoic acid (PFOA, 2.67-7.83 ng L(-1)) dominated. The rivers Elbe, Weser and Ems had a high influence on the distribution of most PFCs in the German Bight, with maximum PFC concentrations found in their estuaries, and concentrations decreasing with increasing distance from the coast. Conversely, PFBS had its maximum concentration not in the estuaries but in the western German Bight, which suggest an additional source, where PFBS was transported into the German Bight with the westerly current.

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in liver samples from harbor seals (Phoca vitulina) collected from the German Bight (1999-2008). Concentrations of various PFCs, including C(4)-C(10) perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfinate (PFOSi), perfluorooctane sulfonamide (FOSA) and C(8)-C(15) perfluoroalkyl carboxylic acids (PFCAs) were quantified. Perfluorooctane sulfonate (PFOS) was the predominant compound with a maximum concentration of 3676 ng g(-1) ww (1996), making up on average 94% of the measured PFCs. Significantly higher concentrations were found in <7 month old in comparison to >or=7 month old harbor seals for C(6)-C(8) PFSAs, perfluorododecanoic acid (PFDoDA) and FOSA, whereas perfluorodecanoic acid (PFDA) showed significantly lower concentrations in the younger harbor seals (p<0.05). These results suggest a transplacental transfer of PFCs to the foetus and/or consumption of different contaminated food. Regression analysis of logarithmic transformed PFC mean concentrations indicated a significant temporal trend with decreasing concentrations for C(5)-C(7) PFSAs (p<0.001), PFOSi (p=0.028), FOSA (p<0.001) and perfluorooctanoic acid (PFOA) (p=0.031) between 1999 and 2008. Furthermore, PFOS decreased by 49% between 1999 and 2008, which correspond with decreasing concentration levels of its metabolic precursors PFOSi and FOSA of 83% and 95% in the same time period. However, the decreasing trend of PFOS is not significant (p=0.067). The reason for the decline during the past 10 years could be an effect of the replacement of these PFCs by shorter chained and less bioaccumulative compounds. But the observations of increasing perfluorodecane sulfonate (PFDS) levels (p=0.070), the high concentrations of PFOS and constant levels of C(9)-C(13) PFCAs indicates that further work on the reduction of environmental emissions of PFCs are necessary.

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.

Total body burden and tissue distribution of polyfluorinated compounds (PFCs) were investigated in harbor seals (Phoca vitulina) from the German Bight in 2007. A total number of 18 individual PFCs from the following groups could be quantified in the different tissues: perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs) and their precursors perfluorinated sulfinates (PFSiAs), perfluorinated sulfonamides, and sulfonamido ethanols. Perfluorooctanesulfonate (PFOS) was the predominant compound in all measured seal tissues (up to 1665 ng g(-1) wet weight in liver tissue). The dominant PFCAs were perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA), but their concentrations were much lower compared to PFOS. The mean whole body burden in harbor seals of all detected PFCs was estimated to be 2665+/-1207 microg absolute. The major amount of the total PFCs burden in the bodies was in blood (38%) and liver (36%), followed by muscle (13%), lung (8%), kidney (2%), blubber (2%), heart (1%), brain (1%), thymus (<0.01%) and thyroid (<0.01%). These data suggest large differences in body burden and accumulation pattern of PFCs in marine mammals.

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.

This article describes the optimisation and validation of an analytical method for the determination of volatile polyfluorinated alkyl substances (PFAS) in environmental air samples. Airborne fluorinated telomer alcohols (FTOHs) as well as fluorinated sulfonamides and sulfonamidoethanols (FOSAs/FOSEs) were enriched on glass-fibre filters (GFFs), polyurethane foams (PUFs) and XAD-2 resin by means of high-volume air samplers. Sensitive and selective determination was performed using gas chromatography/chemical ionisation-mass spectrometry (GC/CI-MS). Five mass-labelled internal standard (IS) compounds were applied to ensure the accuracy of the analytical results. No major blank problems were encountered. Recovery experiments were performed, showing losses of the most volatile compounds during extraction and extract concentration as well as strong signal enhancement for FOSEs due to matrix effects. Breakthrough experiments revealed losses of the most volatile FTOHs during sampling, while FOSAs/FOSEs were quantitatively retained. Both analyte losses and matrix effects could be remediated by application of adequate mass-labelled IS. Method quantification limits (MQLs) of the optimised method ranged from 0.2 to 2.5 pg/m(3) for individual target compounds. As part of the method validation, an interlaboratory comparison of instrumental quantification methods was conducted. The applicability of the method was demonstrated by means of environmental air samples from an urban and a rural location in Northern Germany.

The Brookhaven Relativistic Heavy Ion Collider (RHIC) has been providing collisions of polarized protons at a beam energy of 100 GeV since 2001. Equipped with two full Siberian snakes in each ring, polarization is preserved during acceleration from injection to 100 GeV. However, the intrinsic spin resonances beyond 100 GeV are about a factor of 2 stronger than those below 100 GeV making it important to examine the impact of these strong intrinsic spin resonances on polarization survival and the tolerance for vertical orbit distortions. Polarized protons were first accelerated to the record energy of 205 GeV in RHIC with a significant polarization measured at top energy in 2005. This Letter presents the results and discusses the sensitivity of the polarization survival to orbit distortions.

At the University of Iowa we devised a learning experience, called the Nutrition and Fitness Program, for third-year medical students. The program was designed to raise awareness of the role of nutrition and exercise in the prevention and treatment of disease. Students spent one afternoon learning about their personal health risk factors, such as body mass index, percent body fat, other anthropometric measures such as waist, hip and mid-arm circumference, blood lipids, bone-mass density, dietary analysis, and fitness assessment. Students spent another afternoon visiting the cardiac rehabilitation center. At the end of each rotation, students gathered for a heart-healthy meal that served as a focus for a discussion with dietitians about important nutrition issues. The literature and our work with medical students support the need and acceptance of a personalized, practical approach to nutrition education. By offering medical students the opportunity to learn about their own nutrition and fitness risk factors, this Nutrition and Fitness Program appears to have played an important role in the students' medical education by narrowing the gap between the "science of nutrition" and the "application of nutrition". Students appreciated learning more about their own health factors and felt that personalizing the information made the learning more valuable and would help in counseling their future patients more effectively.

Reducing red meat intake to lower serum cholesterol may also lower iron and zinc intake. Eighty-six seventh and eighth graders who enrolled in a study comparing serum ferritin, zinc, and cholesterol levels were randomized to a low-fat eating pattern emphasizing either lean beef or lean poultry and fish. Serum data and three 24-hour recalls were collected at baseline and 3 months. The lean beef group ate significantly more beef [26 (4, 37) g/d; P<.01] and both groups reduced total and saturated fat intake. Although serum ferritin level change between baseline and intervention was significantly different between the lean beef and lean poultry and fish groups (median [interquartile range] 0.7 [-6, 8] and -6.8 [-12, 2] microg/dL, respectively), the drop in the lean poultry and fish group was not clinically significant. No differences were observed in iron and zinc intake or in serum zinc and cholesterol levels. Teenagers eating diets low in saturated fat may benefit from adequate amounts of lean red meat.

A new type of spin depolarization resonance has been observed at the Brookhaven Alternating Gradient Synchrotron (AGS). This spin resonance is identified as a strong closed-orbit sideband around the dominant intrinsic spin resonance. The strength of the resonance was proportional to the 9th harmonic component of the horizontal closed orbit and proportional to the vertical betatron oscillation amplitude. This "hybrid" spin resonance cannot be overcome by the partial snake at the AGS, but it can be corrected by the harmonic orbit correctors.

Motivational interviewing offers health care professionals a potentially effective strategy for increasing a patient's readiness to change health behaviors. Recently, elements of motivational interviewing and the stages of change model have been simplified and adapted for use with patients in brief clinical encounters. This paper describes in detail a brief motivational intervention model to improve and renew dietary adherence with adolescents in the Dietary Intervention Study in Children (DISC). DISC is a randomized, multi-center clinical trial assessing the efficacy and safety of lowering dietary fat to decrease low-density lipoprotein cholesterol in high-risk children. In the first 3 years of follow-up covering ages 8-13, intervention participants (n = 334) were exposed to a family-based group intervention approach to change dietary choices. To address adherence and retention obstacles as participants moved into adolescence (age 13-17), an individual-level motivational intervention was implemented. The DISC motivational intervention integrates several intervention models: stages of change, motivational interviewing, brief negotiation and behavioral self-management. A preliminary test of the intervention model suggests that it was acceptable to the participants, popular with interventionists and appeared to be an age-appropriate shift from a family-based intervention model.

Out of 865 homosexual males who were registered by venerologists in 6 districts of the GDR highly significantly more homosexuals were born during the stressful war and early postwar period of the Second World War, i.e. between 1941 and 1947 (with a maximum of relative frequency in 1944-1945), than in the years before or after this critical period. This finding suggests that stressful prenatal (or perinatal) events may represent an aetiogenetic factor for homosexuality in human males.

Total and free plasma testosterone (T) were determined in male homosexuals. While total T showed no significant difference to a heterosexual control group, apparently free T in plasma was significantly lower (p less than 0.001) in 35 male homosexuals (mean +/- SD = 10.7 +/- 3.3 ng/100 ml) than in 38 male heterosexuals of similar age (13.3 +/- 4.5 ng/100 ml).