Degradation of fluorotelomer alcohols: a likely atmospheric source of perfluorinated carboxylic acids

Human and animal tissues collected in urban and remote global locations contain persistent and bioaccumulative perfluorinated carboxylic acids (PFCAs). The source of PFCAs was previously unknown. Here we present smog chamber studies that indicate fluorotelomer alcohols (FTOHs) can degrade in the atmosphere to yield a homologous series of PFCAs. Atmospheric degradation of FTOHs is likely to contribute to the widespread dissemination of PFCAs. After their bioaccumulation potential is accounted for, the pattern of PFCAs yielded from FTOHs could account for the distinct contamination profile of PFCAs observed in arctic animals. Furthermore, polar bear liver was shown to contain predominately linear isomers (>99%) of perfluorononanoic acid (PFNA), while both branched and linear isomers were observed for perfluorooctanoic acid, strongly suggesting a sole input of PFNA from "telomer"-based products. The significance of the gas-phase peroxy radical cross reactions that produce PFCAs has not been recognized previously. Such reactions are expected to occur during the atmospheric degradation of all polyfluorinated materials, necessitating a reexamination of the environmental fate and impact of this important class of industrial chemicals.     

Biomagnification of perfluorinated compounds in a remote terrestrial food chain: Lichen-Caribou-wolf

The biomagnification behavior of perfluorinated carboxylates (PFCAs) and perfluorinated sulfonates (PFSAs) was studied in terrestrial food webs consisting of lichen and plants, caribou, and wolves from two remote northern areas in Canada. Six PFCAs with eight to thirteen carbons and perfluorooctane sulfonate (PFOS) were regularly detected in all species. Lowest concentrations were found for vegetation (0.02-0.26 ng/g wet weight (ww) sum (Σ) PFCAs and 0.002-0.038 ng/g ww PFOS). Wolf liver showed highest concentrations (10-18 ng/g ww ΣPFCAs and 1.4-1.7 ng/g ww PFOS) followed by caribou liver (6-10 ng/g ww ΣPFCAs and 0.7-2.2 ng/g ww PFOS). Biomagnification factors were highly tissue and substance specific. Therefore, individual whole body concentrations were calculated and used for biomagnification and trophic magnification assessment. Trophic magnification factors (TMF) were highest for PFCAs with nine to eleven carbons (TMF = 2.2-2.9) as well as PFOS (TMF = 2.3-2.6) and all but perfluorooctanoate were significantly biomagnified. The relationship of PFCA and PFSA TMFs with the chain length in the terrestrial food chain was similar to previous studies for Arctic marine mammal food web, but the absolute values of TMFs were around two times lower for this study than in the marine environment. This study demonstrates that challenges remain for applying the TMF approach to studies of biomagnification of PFCAs and PFSAs, especially for terrestrial animals.     

Anti-inflammatory effect of the extract from fermented <Emphasis Type="Italic">Asterina pectinifera</Emphasis> with <Emphasis Type="Italic">Cordyceps militaris</Emphasis> mycelia in LPS-induced RAW264.7 macrophages

In our previous work, Asterina pectinifera was fermented with Cordyceps militaris mycelia to improve its bioactivities and was reported to have strong antioxidant activities. The aim of the current study was to investigate its anti-inflammatory effect and mechanisms of action. In this study, we observed the inhibitory effect of the extract from fermented A. pectinifera with C. militaris mycelia (FACM) on nitric oxide (NO) production and its molecular mechanism in lipopolysaccharide (LPS)-stimulated RAW264.7 cells. FACM could decrease LPS-induced NO production. Western blot analysis showed that FACM could down-regulate LPS-induced expression of inducible NO synthase without affecting cyclooxygenase-2. Moreover, FACM exhibited anti-inflammatory activity in LPS-induced RAW264.7 mouse macrophage cells through proinflammatory mediators including TNF-α and IL-6 via nuclear factor kappa B pathway. FACM inhibited LPS-induced phosphorylation of extracellular-signal-regulated kinase expression. Our results suggest that FACM may be a potential candidate for inflammation therapy by attenuating the generation of cytokines, production of NO, and generation of ROS in RAW264.7 cells.     

Monitoring of perfluorinated compounds in aquatic biota: an updated review

The goal of this article is to summarize new biological monitoring information on perfluorinated compounds (PFCs) in aquatic ecosystems (post-2005) as a followup to our critical review published in 2006. A wider range of geographical locations (e.g., South America, Russia, Antarctica) and habitats (e.g., high-mountain lakes, deep-ocean, and offshore waters) have been investigated in recent years enabling a better understanding of the global distribution of PFCs in aquatic organisms. High concentrations of PFCs continue to be detected in invertebrates, fish, reptiles, and marine mammals worldwide. Perfluorooctane sulfonate (PFOS) is still the predominant PFC detected (mean concentrations up to 1900 ng/g ww) in addition to important concentrations of long-chain perfluoroalkyl carboxylates (PFCAs; sum PFCAs up to 400 ng/g ww). More studies have evaluated the bioaccumulation and biomagnification of these compounds in both freshwater and marine food webs. Several reports have indicated a decrease in PFOS levels over time in contrast to PFCA concentrations that have tended to increase in tissues of aquatic organisms at many locations. The detection of precursor metabolites and isomers has become more frequently reported in environmental assessments yielding important information on the sources and distribution of these contaminants. The integration of environmental/ecological characteristics (e.g., latitude/longitude, salinity, and/or trophic status at sampling locations) and biological variables (e.g., age, gender, life cycle, migration, diet composition, growth rate, food chain length, metabolism, and elimination) are essential elements in order to adequately study the environmental fate and distribution of PFCs and should be more frequently considered in study design.     

Impact of human Campylobacter infections in Southeast Asia: The contribution of the poultry sector

Campylobacter is globally recognized as a major cause of foodborne infection in humans, whilst the development of antimicrobial resistance and the possibility of repelling therapy increase the threat to public health. Poultry is the most frequent source of Campylobacter infection in humans, and southeast Asia is a global leader in poultry production, consumption, and exports. Though three of the world's top 20 most populated countries are located in southeast Asia, the true burden of Campylobacter infection in the region has not been fully elucidated. Based on published data, Campylobacter has been reported in humans, animals, and food commodities in the region. To our knowledge, this study is the first to review the status of human Campylobacter infection in southeast Asia and to discuss future perspectives. Gaining insight into the true burden of the infection and prevalence levels of Campylobacter spp. in the southeast Asian region is essential to ensuring global and regional food safety through facilitating improvements in surveillance systems, food safety regulations, and mitigation strategies.     

Enantiospecific perfluorooctane sulfonate (PFOS) analysis reveals evidence for the source contribution of PFOS-precursors to the Lake Ontario foodweb

Exposure to perfluorooctane sulfonate (PFOS) may arise directly, from emission and exposure to PFOS itself, or indirectly via the environmental release and degradation of PFOS-precursors. Human serum enantiomer fractions (EFs) of 1m-PFOS have been shown to be nonracemic, suggesting that PFOS-precursors are a significant source of PFOS in humans, but little is known about the importance of PFOS-precursors in ecosystems. In the current work, concentrations of PFOS, perfluorooctane sulfonamide (PFOSA), PFOS isomer profiles, and EFs of 1m-PFOS were determined in Lake Ontario water, sediment, fishes and invertebrates. Concentrations of PFOS and PFOSA were highest in slimy sculpin and Diporeia, and concentrations of the two compounds were often correlated. 1m-PFOS was racemic in sediment, water, sculpin and rainbow smelt, but nonracemic in the top predator, lake trout, and all invertebrate species. Furthermore, EFs were correlated with the relative concentrations of PFOS and PFOSA in invertebrates. Overall, these empirical observations with a new analytical tool confirm previous suggestions that PFOS-precursors contribute to PFOS in the food web, likely via sediment. Implications are that future PFOS exposures in this ecosystem will be influenced by an in situ source, and that the apparent environmental behavior of PFOS (e.g., bioaccumulation potential) can be confounded by precursors.     

Isomer distribution of perfluorocarboxylates in human blood: potential correlation to source

Detection of perfluorocarboxylate anions (PFCAs), such as perfluorooctanoate (C7F15COO-, PFOA), at ng/g levels in human tissues has engendered public scrutiny of industrial fluorochemicals. Routes of PFCA exposure for the general human population are likely diverse given direct (industrially produced) and indirect (production from precursor organofluorines) sources. Major industrial production of organofluorines, including PFCAs, stems from either electrochemical fluorination (ECF) or telomerization. ECF products are a mixture of structural isomers (linear and branched perfluoroalkyls) and telomerization products are assumed to have one perfluorocarbon arrangement, typically linear. The objective of this research was to investigate structural isomer patterns of PFCAs in human blood. Volatile derivatives of PFCAs in human blood were analyzed by GC-(NCI)-MS for quantitation and isomers. PFOA was the dominant PFCA (mean 4.4 ng/g). Blood serum isomer profiles consisted of predominantly (mean approximately 98%) the linear isomer for each PFCA (C8-C11). There were similarities in branched isomer patterns of an ECF PFOA standard with both PFOA and PFNA in blood. Direct exposure to ECF PFOA, which has a legacy of production for uses in fluoropolymer industries, is postulated to be a source of the observed branched isomer pattern. Predominance of linear PFCA isomers and the [even PFCA] > [odd PFCA] concentration trend in blood is suggestive of additional input from a strictly linear perfluoroalkyl source.     

Detection of a cyclic perfluorinated acid, perfluoroethylcyclohexane sulfonate, in the Great Lakes of North America

Perfluoroethylcyclohexanesulfonate (PFECHS) is a cyclic perfluorinated acid (PFA) mainly used as an erosion inhibitor in aircraft hydraulic fluids. It is expected to be as recalcitrant to environmental degradation as aliphatic PFAs including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). For the first time, PFECHS is reported in top predator fish (相似文献   

Enhancing low-temperature energy harvesting by lead-free ferroelectric Ba(Zr0.1Ti0.9)O3

The energy-harvesting ability of the lead-free ferroelectric Ba(Zr,Ti)O₃ was investigated and greatly enhanced using the Kim novel electrothermodynamic cycle for low-temperature application. Ba(Zr,Ti)O₃ was synthesized with a Zr:Ti ratio of 10:90 (BZT10) by hot-press sintering, which exhibited a mix relaxor-ferroelectric behavior. For power generation using the Kim cycle with low and high temperatures of T_L = 25°C, T_H = 120°C, the most optimized temperature pattern occurred for a heating time of 12.5 s and a cooling time of 22.5 s. Under these conditions, the electric field increased during the novel isodisplacement process, and the displacement variation in the isoelectric step reached the highest value and maximized the BZT10 cycle loop area. Applying these conditions while lowering T_L to 20°C, an energy density N_D = 504 mJ/cm³ was achieved. This value is the highest obtained energy density in a practical test for lead-free ferroelectric bulk material in the BaTiO₃ family.