全氟辛酸和全氟辛烷磺酸异构体的膳食暴露来源
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摘要
本研究采用超高效液相色谱串联三重四级杆质谱法测定了福建省当地居民血清和总膳食样品中全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)典型异构体的污染水平,并分析了血清和膳食中PFOA和PFOS支链/直链的比例,初步探讨了当地居民支链PFOA和PFOS的膳食暴露来源.结果表明,在所有血清样品中均可检出n-PFOA和n-PFOS,其中位数浓度水平分别为3.7 ng·mL~(-1)和7.0 ng·mL~(-1),且血清中检出了5种PFOS支链异构体和1种PFOA支链异构体.血清中n-PFOA占total-PFOA的比例(99.81%)和n-PFOS占total-PFOS的比例(84.56%)均显著高于目前市场上销售的PFOA和PFOS工业品.而对于膳食样品,仅在乳类膳食中检出2种支链PFOA异构体,未在膳食样品中检出PFOS支链异构体.血清和膳食样品中不同的支链/直链PFOA和PFOS的比例对比结果表明:乳类膳食有可能是福建省居民暴露于支链PFOA异构体(br-PFOA)的重要来源,支链PFOS异构体(br-PFOS)可能存在膳食暴露之外的重要暴露途径.
Levels of PFOA,PFOS and their isomers in the serum and the total diet study(TDS)samples from Fujian were detected by ultra-performance liquid chromatography coupled with tandem mass spectrometry.The percentage and the dietary source of human exposure to the branched/linear isomers of PFOA and PFOS were analyzed.n-PFOA and n-PFOS were detected in any serum sample,with the median concentration of 3.7 ng·mL~(-1) and 7.0 ng·mL~(-1),respectively.Five branched isomers of PFOS were detected,and only one branched isomer of PFOA was detected in the serum.The percentage of n-PFOA to total-PFOA(99.81%) and n-PFOS to total-PFOS(84.56%) in serum were significantly higher than that in PFOA and PFOS industrial products.And two branched isomers of PFOA were detected in the milk samples,whereas no branched isomers of PFOS were detected in any diet sample.The results of the comparison of the percentage of branched/linear isomers of PFOA and PFOS between serum and diet samples indicated that the intake of milkmay be an important source of human exposure to br-PFOA.In addition to diet intake,there may be other important sources of human exposure to br-PFOS.
Levels of PFOA,PFOS and their isomers in the serum and the total diet study(TDS)samples from Fujian were detected by ultra-performance liquid chromatography coupled with tandem mass spectrometry.The percentage and the dietary source of human exposure to the branched/linear isomers of PFOA and PFOS were analyzed.n-PFOA and n-PFOS were detected in any serum sample,with the median concentration of 3.7 ng·mL~(-1) and 7.0 ng·mL~(-1),respectively.Five branched isomers of PFOS were detected,and only one branched isomer of PFOA was detected in the serum.The percentage of n-PFOA to total-PFOA(99.81%) and n-PFOS to total-PFOS(84.56%) in serum were significantly higher than that in PFOA and PFOS industrial products.And two branched isomers of PFOA were detected in the milk samples,whereas no branched isomers of PFOS were detected in any diet sample.The results of the comparison of the percentage of branched/linear isomers of PFOA and PFOS between serum and diet samples indicated that the intake of milkmay be an important source of human exposure to br-PFOA.In addition to diet intake,there may be other important sources of human exposure to br-PFOS.
引文
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[31]SHAN G,WANG Z,ZHOU L,et al.Impacts of daily intakes on the isomeric profiles of perfluoroalkyl substances(PFASs)in human serum.[J].Environment International,2016,89-90(20):62-70.
[32]GEBBINK W A,BERGER U,COUSINS I T.Estimating human exposure to PFOS isomers and PFCA homologues:the relative importance of direct and indirect(precursor)exposure[J].Environment International,2015,74:160-169.
[33]MIRALLES-MARCO A,HARRAD S.Perfluorooctane sulfonate:A review of human exposure,biomonitoring and the environmental forensics utility of its chirality and isomer distribution[J].Environment International,2015,77:148-159.
[2]胡存丽,仲来福.全氟辛烷磺酸和全氟辛酸毒理学研究进展[J].中国工业医学杂志,2006,19(6):354-358.HU C L,ZHONG L F.Progress of toxicological study on PFOS and PFOA[J].Chinese Journal of Industrial Medicine,2006,19(6):354-358(in Chinese).
[3]MINGHONG C,ZHEN Z,HAIZHEN Y,et al.Spatial distribution of per-and polyfluoroalkyl compounds in coastal waters from the East to South China Sea[J].Environmental Pollution,2012,161(1):162-169.
[4]WANG P,WANG T,GIESY J P,et al.Perfluorinated compounds in soils from Liaodong Bay with concentrated fluorine industry parks in China[J].Chemosphere,2013,91(6):751-757.
[5]ZHAO Y G,WAN H T,LAW A Y S,et al.Risk assessment for human consumption of perfluorinated compound-contaminated freshwater and marine fish from Hong Kong and Xiamen[J].Chemosphere,2011,85(2):277-283.
[6]DOMINGO J L,ERICSONJOGSTEN I,PERELLO G,et al.Human Exposure to Perfluorinated Compounds in Catalonia,Spain:Contribution of Drinking Water and Fish and Shellfish[J].Journal of Agricultural&Food Chemistry,2012,60(17):4408-4415.
[7]MUNSCHY C,MARCHAND P,VENISSEAU A,et al.Levels and trends of the emerging contaminants HBCDs(hexabromocyclododecanes)and PFCs(perfluorinated compounds)in marine shellfish along French coasts.[J].Chemosphere,2013,91(2):233-240.
[8]GUERRANTI C,ANCORA S,BIANCHI N,et al.Perfluorinated compounds in blood of Caretta caretta,from the Mediterranean Sea[J].Marine Pollution Bulletin,2013,73(1):98-101.
[9]GUO F,ZHONG Y,WANG Y,et al.Perfluorinated compounds in human blood around Bohai Sea,China.[J].Chemosphere,2011,85(2):156-162.
[10]JI K,KIM S,KHO Y,et al.Serum concentrations of major perfluorinated compounds among the general population in Korea:Dietary sources and potential impact on thyroid hormones.[J].Environment International,2012,45(1):78-85.
[11]BARBAROSSA A,MASETTI R,GAZZOTTI T,et al.Perfluoroalkyl substances in human milk:A first survey in Italy[J].Environment International,2013,51(51C):27-30.
[12]RAAB U,ALBRECHT M,PREISS U,et al.Organochlorine compounds,nitro musks and perfluorinated substances in breast milk-results from Bavarian Monitoring of Breast Milk 2007/8[J].Chemosphere,2013,93(3):461-467.
[13]LIU J,LI J,LIU Y,et al.Comparison on gestation and lactation exposure of perfluorinated compounds for newborns[J].Environment International,2011,37(7):1206-1212.
[14]LIU J,LI J,ZHAO Y,et al.The occurrence of perfluorinated alkyl compounds in human milk from different regions of China[J].Environment International,2010,36(5):433-438.
[15]WU Y,WANG Y,LI J,et al.Perfluorinated compounds in seafood from coastal areas in China[J].Environment International,2012,42:67-71.
[16]TITTLEMIER S A,PEPPER K,SEYMOUR C,et al.Dietary exposure of canadians to perfluorinated carboxylates and perfluorooctane sulfonate via consumption of meat,fish,fast foods,and food items prepared in their packaging.[J].Journal of Agricultural&Food Chemistry,2007,55(8):3203-3210.
[17]ERICSON I,MARTICID R,NADAL M,et al.Human exposure to perfluorinated chemicals through the diet:Intake of perfluorinated compounds in foods from the Catalan(Spain)market[J].Journal of Agricultural&Food Chemistry,2008,56(5):1787-1794.
[18]Prevedouros K,Cousins I T,Buck R C,et al.Sources,fate and transport of perfluorocarboxylates[J].Environmental Science&Technology,2006,40(1):32-44.
[19]张义峰,赵丽霞,单国强,等.全氟化合物同分异构体的环境行为及毒性效应研究进展[J].生态毒理学报,2012,7(5):464-476.ZHANG Y F,ZHAO L X,SHAN G Q,et al.Advances in studies on environmental behaviors and toxic effects of perfluoroalkyl substance isomers[J].Asian Journal of Ecotoxicology,2012,7(5):464-476(in Chinese).
[20]BENSKIN J P,BATAINEH M,MARTIN J W.Simultaneous characterization of perfluoroalkyl carboxylate,sulfonate,and sulfonamide isomers by liquid chromatographytandem mass spectrometry[J].Analytical Chemistry,2007,79(17):6455-6464.
[21]吴永宁,李筱薇.第四次中国总膳食研究[M].北京:化学工业出版社,2015.WU Y N,LI X W.The Fourth China Total Diet Study[M].Beijing:Chemical Industry Press,2015(in Chinese).
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[23]JIANG W,ZHANG Y,YANG L,et al.Perfluoroalkyl acids(PFAAs)with isomer analysis in the commercial PFOS and PFOA products in China[J].Chemosphere,2015,127:180-187.
[24]ZHANG Y,JIANG W,FANG S,et al.Perfluoroalkyl acids and the isomers of perfluorooctanesulfonate and perfluorooctanoate in the sera of50 new couples in Tianjin,China[J].Environment International,2014,68:185-191.
[25]ZHANG Y,BEESOON S,ZHU L,et al.Isomers of perfluorooctanesulfonate and perfluorooctanoate and total perfluoroalkyl acids in human serum from two cities in North China[J].Environment International,2013,53(2):9-17.
[26]JIN H,ZHANG Y,JIANG W,et al.Isomer-specific distribution of perfluoroalkyl substances in blood.[J].Environmental Science&Technology,2016,50:7808-7815.
[27]CHEN F,YIN S,KELLY B C,et al.Isomer-specific transplacental transfer of perfluoroalkyl acids:Results from a survey of paired maternal,cord sera and placentas.[J].Environmental Science&Technology,2017,51(10):5756-5763.
[28]BEESOON S,WEBSTER G M,SHOEIB M,et al.Isomer profiles of perfluorochemicals in matched maternal,cord,and house dust samples:manufacturing sources and transplacental transfer[J].Environmental Health Perspectives,2011,119(11):1659-1664.
[29]GEBBINK W A,LETCHER R J.Linear and branched perfluorooctane sulfonate isomer patterns in herring gull eggs from colonial sites across the Laurentian Great Lakes[J].Environmental Science&Technology,2010,44(10):3739-3745.
[30]POWLEY C R,GEORGE S W,RUSSELL M H,et al.Polyfluorinated chemicals in a spatially and temporally integrated food web in the Western Arctic[J].Chemosphere,2008,70(4):664-672.
[31]SHAN G,WANG Z,ZHOU L,et al.Impacts of daily intakes on the isomeric profiles of perfluoroalkyl substances(PFASs)in human serum.[J].Environment International,2016,89-90(20):62-70.
[32]GEBBINK W A,BERGER U,COUSINS I T.Estimating human exposure to PFOS isomers and PFCA homologues:the relative importance of direct and indirect(precursor)exposure[J].Environment International,2015,74:160-169.
[33]MIRALLES-MARCO A,HARRAD S.Perfluorooctane sulfonate:A review of human exposure,biomonitoring and the environmental forensics utility of its chirality and isomer distribution[J].Environment International,2015,77:148-159.