Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging—method development and screening

Polyfluoroalkyl phosphate mono-, di-, and tri-esters (mono-, di-, and triPAPs) are used to water- and grease-proof food packaging materials, and these chemicals are known precursors to perfluoroalkyl carboxylic acids (PFCAs). Existing analytical methods for PAPs lack sample clean-up steps in the sample preparation. In the present study, a method based on ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS) was developed and optimized for the analysis of mono-, di-, and triPAPs, including a clean-up step for the raw extracts. The method was applied to food samples and their PAP-containing packaging materials. The optimized UPLC/MS/MS method enabled the separation and identification of a total of 4 monoPAPs, 16 diPAPs, and 7 triPAPs in the technical mixture Zonyl®-RP. For sample clean-up, weak anion exchange solid phase extraction columns were tested. PAPs standard solutions spiked onto the columns were separated into a fraction containing neutral compounds (triPAPs) and a fraction with ionic compounds (mono- and diPAPs) with recoveries between 72–110 %. Method limits of quantification for food samples were in the sub to low picogram per gram range. For quantitative analysis of PAPs, compound-specific labeled internal standards showed to be essential as sorption and matrix effects were observed. Mono-, di-, and/or triPAPs were detected in all food packaging materials obtained from the Swedish market. Up to nine diPAPs were detected in the food samples, with the 6:2/6:2 and 6:2/8:2 diPAPs as the dominant compounds. DiPAP concentrations in the food samples ranged from 0.9 to 36 pg/g, which was comparable to individual PFCA concentrations in the same samples. Consumption of food packed in PAP-containing materials could be an indirect source of human exposure to PFCAs.     

Perfluoroalkyl carboxylates and sulfonates and precursors in relation to dietary source tracers in the eggs of four species of gulls (Larids) from breeding sites spanning Atlantic to Pacific Canada

In the present study, we identified and examined the spatial trends, sources and dietary relationships of bioaccumulative perfluorinated sulfonate (PFSA; C(6), C(8), and C(10) chain lengths) and carboxylate (PFCA; C(6) to C(15) chain lengths) contaminants, as well as precursor compounds including several perfluorinated sulfonamides, and fluorotelomer acids and alcohols, in individual eggs (collected in 2008) from four gull species [glaucous-winged (Larus glaucescens), California (Larus californicus), ring-billed (Larus delawarensis) and herring (Larus argentatus) gulls] from 15 marine and freshwater colony sites in provinces across Canada. The pattern of PFSAs was dominated by perfluorooctane sulfonate (PFOS; >89% of ΣPFSA concentration) regardless of egg collection location. The highest ΣPFSA concentrations were found in the eggs collected in the urbanized areas in the Great Lakes and the St. Lawrence River area [Big Chicken Island 308 ng/g ww, Toronto Harbour 486 ng/g ww, and Ile Deslauriers (HG) 299 ng/g ww]. Also, eggs from all freshwater colony sites had higher ΣPFSA concentrations, which were significant (p<0.05) in many cases, compared to the marine sites with the exception of the Sable Island colony in Atlantic Canada off the coast of Nova Scotia. C(6) to C(15) chain length PFCAs were detected in the eggs, although the pattern was variable among the 15 sites, where PFUnA and PFTrA dominated the pattern for most colonies. Like the ΣPFSA, the highest concentrations of ΣPFCA were found in the eggs from Big Chicken Island, Toronto Harbour, Ile Deslauriers (HG), and Sable Island, although not all freshwater sites had higher concentrations compared to marine sites. Dietary tracers [δ(15)N and δ(13)C stable isotopes (SIs)] revealed that PFSA and PFCA exposure is colony dependent. SI signatures suggested that gulls from most marine colony sites were exposed to PFCs via marine prey. The exception was the Mandarte Island colony in Pacific British Columbia, where PFSA and PFCA exposure appeared to be via terrestrial and/or freshwater prey consumption. The same was true for the freshwater sites where egg SIs suggested both aquatic and terrestrial prey consumption as the source for PFC exposure depending on the colony. Both aquatic (marine and freshwater) and terrestrial prey are likely sources of PFC exposure to gulls but exposure scenarios are colony-specific.     

Organohalogen contaminants and metabolites in cerebrospinal fluid and cerebellum gray matter in short-beaked common dolphins and Atlantic white-sided dolphins from the western North Atlantic

Concentrations of several congeners and classes of organohalogen contaminants (OHCs) and/or their metabolites, namely organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), hydroxylated-PCBs (OH-PCBs), methylsulfonyl-PCBs (MeSO₂-PCBs), polybrominated diphenyl ether (PBDE) flame retardants, and OH-PBDEs, were measured in cerebrospinal fluid (CSF) of short-beaked common dolphins (n = 2), Atlantic white-sided dolphins (n = 8), and gray seal (n = 1) from the western North Atlantic. In three Atlantic white-sided dolphins, cerebellum gray matter (GM) was also analyzed. The levels of OCs, PCBs, MeSO₂-PCBs, PBDEs, and OH-PBDEs in cerebellum GM were higher than the concentrations in CSF. 4-OH-2,3,3′,4′,5-pentachlorobiphenyl (4-OH-CB107) was the only detectable OH-PCB congener present in CSF. The sum (Σ) OH-PCBs/Σ PCB concentration ratio in CSF was approximately two to three orders of magnitude greater than the ratio in cerebellum GM for dolphins.     

Tissue-specific congener composition of organohalogen and metabolite contaminants in East Greenland polar bears (Ursus maritimus)

Congener patterns of the major organohalogen contaminant classes of PCBs, PBDEs and their metabolites and/or by-products (OH-PCBs, MeSO2-PCBs, OH-PBDEs and MeO-PBDEs) were examined in adipose tissue, liver, brain and blood of East Greenland polar bears (Ursus maritimus). PCB, OH-PCB, MeSO2-PCB and PBDE congener patterns showed significant differences (p相似文献   

Twenty years of temporal change in perfluoroalkyl sulfonate and carboxylate contaminants in herring gull eggs from the Laurentian Great Lakes

In this study, temporal trends and patterns of major C(4) to C(15) chain length PFCAs and PFSAs and some sulfonamide, fluorotelomer acid and alcohol precursors were determined in herring gull (Larus argentatus) egg pools. Samples were analyzed from fifteen collection years including 1990 and all years from 1997 to 2010, and from seven colonies located throughout the Great Lakes, ranging from remote to highly urbanized areas. Other than at the Toronto Harbour colony, the slopes of ∑PFSA concentrations (C(6), C(8), and C(10)) versus time were negative indicating general declines between 1990 and 2010. PFOS was the dominant PFSA regardless of colony or year, ranging from 80 to 99% of ∑PFSA. For ∑PFCA (C(8)-C(15)), slopes of concentrations versus time were generally positive with 4 of 7 colonies showing statistically significant (p < 0.05) increases in levels through time. Individual PFCAs showed similar increasing trends except for PFOA. Regardless of colony, the PFCA pattern was dominated by the C(10) to C(13) PFCAs. Consistent with the PFOS declines, concentrations of the PFOS precursor, PFOSA, declined at most colonies between 1990 and 2006 and post-2006 concentrations were below detection limits. Declining concentrations of the C(8) PFCs, PFOS, PFOA and PFOSA, were consistent with the phase out in 2002 by the 3M Company in North America of all of C(8) PFC-related chemistry products. Increasing production volumes of fluorotelomer based compounds, and degradation of these compounds to PFCAs may explain increasing trends of PFCAs in gull eggs. Dietary changes as measured by carbon and nitrogen stable isotopes, showed minimal relationships to PFC levels in gull eggs, which indicates the complexity of aquatic and terrestrial food of gulls and sources of PFCs.     

Bioaccumulation and biotransformation of brominated and chlorinated contaminants and their metabolites in ringed seals (Pusa hispida) and polar bears (Ursus maritimus) from East Greenland

We report on the comparative bioaccumulation, biotransformation and/or biomagnification from East Greenland ringed seal (Pusa hispida) blubber to polar bear (Ursus maritimus) tissues (adipose, liver and brain) of various classes and congeners of persistent chlorinated and brominated contaminants and metabolic by-products: polychlorinated biphenyls (PCBs), chlordanes (CHLs), hydroxyl (OH-) and methylsulfonyl (MeSO₂-) PCBs, polybrominated biphenyls (PBBs), OH-PBBs, polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants and OH- and methoxyl (MeO-) PBDEs, 2,2-dichloro-bis(4-chlorophenyl)ethene (p,p′-DDE), 3-MeSO₂-p,p′-DDE, pentachlorophenol (PCP) and 4-OH-heptachlorostyrene (4-OH-HpCS). We detected all of the investigated contaminants in ringed seal blubber with high frequency, the main diet of East Greenland bears, with the exception of OH-PCBs and 4-OH-HpCS, which indicated that these phenolic contaminants were likely of metabolic origin and formed in the bears from accumulated PCBs and octachlorostyrene (OCS), respectively, rather than being bioaccumulated from a seal blubber diet. For all of the detectable sum of classes or individual organohalogens, in general, the ringed seal to polar bear mean BMFs for ΣPCBs, p,p′-DDE, ΣCHLs, ΣMeSO₂-PCBs, 3-MeSO₂-p,p′-DDE, PCP, ΣPBDEs, total-(α)-HBCD, ΣOH-PBDEs, ΣMeO-PBDEs and ΣOH-PBBs indicated that these organohalogens bioaccumulate, and in some cases there was tissue-specific biomagnification, e.g., BMFs for bear adipose and liver ranged from 2 to 570. The blood-brain barrier appeared to be effective in minimizing brain accumulation as BMFs were ≤ 1 in the brain, with the exception of ΣOH-PBBs (mean BMF = 93 ± 54). Unlike OH-PCB metabolites, OH-PBDEs in the bear tissues appeared to be mainly accumulated from the seal blubber rather than being metabolic formed from PBDEs in the bears. In vitro PBDE depletion assays using polar bear hepatic microsomes, wherein the rate of oxidative metabolism of PBDE congeners was very slow, supported the probability that accumulation from seals is the main source of OH-PBDEs in the bear tissues. Our findings demonstrated from ringed seal to polar bears that organohalogen biotransformation, bioaccumulation and/or biomagnification varied widely and depended on the contaminant in question. Our results show the increasing complexity of bioaccumulated and in some cases biomagnified, chlorinated and brominated contaminants and/or metabolites from the diet may be a contributing stress factor in the health of East Greenland polar bears.     

陕西民俗文化旅游资源的保护与开发

陕西民俗文化旅游资源丰富,具有较高的社会价值和旅游价值,但由于政府部门的疏于重视和广大民众认识的浅薄,导致陕西民俗文化旅游资源受到严重的破坏,同时也造成不良风气的大量出现,使这些价值未能得以发挥.针对这一现状,以全国民俗文化的保护和开发为参照,结合陕西民俗文化旅游资源的自身特点,从保护和发展两个方面涉及的具体问题为出发点,就具体的问题提出了具体的建议,希望以此引起各方重视.参5.