气相色谱法检测水产养殖底泥中10种羟基多氯联苯
|
摘要
该研究建立了气相色谱(GC-μECD)检测水产养殖底泥中10种羟基多氯联苯的方法.底泥样品经HCl(6 mol·L~(-1))调节p H值至3.0,以正己烷为提取溶剂,提取液采用固相萃取硅胶柱净化,确定了淋洗液比例及用量等参数,硅胶柱经淋洗后,用正己烷/乙酸乙酯(1∶1,V/V)洗脱,收集洗脱液经氮气吹干后进行硅烷化衍生,气相色谱法检测.研究确定淋洗液为正己烷/乙酸乙酯(98∶2,V/V),用量5 mL;方法检出限4.00μg·kg~(-1),定量限8.00μg·kg~(-1);在4.00、8.00、20.0μg·kg~(-1)的添加水平下,10种羟基多氯联苯的平均回收率为72.4%—94.0%,相对标准偏差(RSD)为1.7%—9.9%,并用于太湖水域实际水产养殖底泥中10种羟基多氯联苯检测分析.结论显示,该方法可用于水产养殖底泥中痕量羟基多氯联苯的检测.
A gas chromatography( GC-μECD) method was established to determine 10 hydroxylated polychlorinated biphenyls in aquaculture sediment. Before extracting with n-hexane,the sediment samples were adjusted to p H 3. 0 with HCl( 6 mol·L~(-1)). In order to remove the interference materials,silica gel column was used for purification,and the proportion and elution volume of the cleaning solvent were optimized simultaneously. After the silica gel column was washed,the target compounds were eluted with n-hexane/ethyl acetate( 1∶1,V/V),and the eluent was proceeded withsilylation derivatization after concentrating under nitrogen fluid. And the target compounds were finally determined by GC-μECD. It was confirmed that the cleaning solvent was n-hexane/ethyl acetate( 98∶2,V/V) with a elution volume of 5 mL. The limit of detection was 4.00 μg·kg~(-1),and the limit of quantitation 8.00 μg·kg~(-1). At spiked levels of 4.00,8.00,20.0 μg·kg~(-1),the average recoveries of 10 hydroxylated polychlorinated biphenyls ranged from 72.4% to 94.0%,RSD ranged from 1.7% to 9. 9%,and this method is used for the analysis of 10 hydroxylated polychlorinated biphenyls in aquaculture sediment from Taihu lake. In conclusion,the method can be used for trace analysis of hydroxylated polychlorinated biphenyls in aquaculture sediment.
A gas chromatography( GC-μECD) method was established to determine 10 hydroxylated polychlorinated biphenyls in aquaculture sediment. Before extracting with n-hexane,the sediment samples were adjusted to p H 3. 0 with HCl( 6 mol·L~(-1)). In order to remove the interference materials,silica gel column was used for purification,and the proportion and elution volume of the cleaning solvent were optimized simultaneously. After the silica gel column was washed,the target compounds were eluted with n-hexane/ethyl acetate( 1∶1,V/V),and the eluent was proceeded withsilylation derivatization after concentrating under nitrogen fluid. And the target compounds were finally determined by GC-μECD. It was confirmed that the cleaning solvent was n-hexane/ethyl acetate( 98∶2,V/V) with a elution volume of 5 mL. The limit of detection was 4.00 μg·kg~(-1),and the limit of quantitation 8.00 μg·kg~(-1). At spiked levels of 4.00,8.00,20.0 μg·kg~(-1),the average recoveries of 10 hydroxylated polychlorinated biphenyls ranged from 72.4% to 94.0%,RSD ranged from 1.7% to 9. 9%,and this method is used for the analysis of 10 hydroxylated polychlorinated biphenyls in aquaculture sediment from Taihu lake. In conclusion,the method can be used for trace analysis of hydroxylated polychlorinated biphenyls in aquaculture sediment.
引文
[1]LETCHERRJ,KLASSON-WEHLERE,BERGMANA.Methyl sulfone and hydroxylated metabolites of polychlorinated biphenyls[J].Volume 3Anthropogenic Compounds Part K,2000,3:315-359.
[2]毕新慧,徐晓白.多氯联苯的环境行为[J].化学进展,2000,12(2):152-160.BI X H,XU X B.Behaviors of PCBs in environment[J].Process in Chemistry,2000,12(2):152-160(in Chinese).
[3]DESMET M,MOURIER B,MAHLER BJ,et al.Spatial and temporal trends in PCBs in sediment along the lower Rh8ne River,France[J].Science of the Total Environment,2012,433:189-197.
[4]NIEWIADOWSKAA,KILJANEK T,SEMENIUK S.Contamination of fish and sediments from the Vistula River by organochlorine pesticides and PCBs[J].Polish Journal of Environmental Studies,2015,24(5):2315-2320.
[5]MOORE M,MUSTAIN M,DANIEL K,et al.Antiestrogenic activity of hydroxylated polychlorinated biphenyl congeners identified in human serum[J].Toxicology and Applied Pharmacology,1997,142(1):160-168.
[6]FIELDEN M,CHENI,CHITTIM B,et al.Examination of the estrogenicity of 2,4,6,2',6'-pentachlorobiphenyl(PCB 104),its hydroxylated metabolite 2,4,6,2',6'-pentachloro-4-biphenylol(HO-PCB 104),and a further chlorinated derivative,2,4,6,2',4',6'-hexachlorobiphenyl(PCB 155)[J].Environmental Health Perspectives,1997,105(11):1238-1248.
[7]MORGADO I,HAMERS T,VEN L V,et al.Disruption of thyroid hormone binding to sea bream recombinant transthyretin by ioxinyl and polybrominated diphenyl ethers[J].Chemosphere,2007,69(1):155-163.
[8]KESTER M,BULDUK S,TIBBOEL D,et al.Potent inhibition of estrogen sulfotransferase by hydroxylated PCB metabolites:a novel pathway explaining the estrogenic activity of PCBs[J].Endocrinology,2000,141(5):1897-1900.
[9]WOODHEAD R J,LAW R J,MATTHIESSEN P.Polycyclic aromatic hydrocarbons in surface sediments around england and wales,and theirpossible biological significance[J].Marine Pollution Bulletin,1999,38(9):773-790.
[10]WINKELS H,LYCHAGIN M,MARIN G,et al.Geochronology of priority pollutants in sedimentation zones of the Volga and Danube delta in comparison with the Rhine delta[J].Applied Geochemistry,1998,13(5):581-591.
[11]WONG C S,CAPELape P D,NOWELL L H.National-scale,field-based evaluation of the biota-sediment accumulation factor model[J].Environmental Science and Technology,2001,35(9):1709-1715.
[12]GEWURTZ S B,GANDHI N,CHRISTENSEN G N,et al.Use of a food web model to evaluate the factors responsible for high PCB fish concentrations in Lake Ellasjoen,a high Arctic Lake[J].Environmental Science&Pollution Research,2009,16(2):176-190.
[13]MORRISON H,GOBAS F,LAZA R,et al.Development and verification of a benthic/pelagic food web bioaccumulation model for PCB congeners in western Lake Erie[J].Environmental Science and Technology,1997,31(11):3267-3273.
[14]LOPES C,PERGA ME,PERETTI A,et al.Is PCBs concentration variability between and within freshwater fish species explained by their contamination pathways?[J].Chemosphere,2011,85(3):502-508.
[15]WOLSKA L.Miniaturised analytical procedure of determining polycyclic aromatic hydrocarbons and polychlorinated biphenyls in bottom sediments[J].Journal of Chromatography A,2002,595(1-2):173-180.
[16]ABRAHAM VM,LYNN J.Determination of hydroxylated polychlorinated biphenyls by ion trap gas chromatography-tandem mass spectrometry[J].Journal of Chromatography A,1997,790(1):131-141.
[17]MARTINEZ A,NORSTR9M K,WANG K,et al.Polychlorinated biphenyls in the surficial sediment of Indiana Harbor and Ship Canal,Lake Michigan[J].Environment International,2010,36(8):849-854.
[18]MAREK R F,THORNE P S,WANG K,et al.PCBs and OH-PCBs in Serum from Children and Mothers in Urban and Rural U.S.Communities[J].Environ Sci Technol,2013,47(7):3353-3361.
[19]MAREK R F,MARTINEZ A,HORNBUCKLE K C.Discovery of hydroxylated polychlorinated biphenyls(OH-PCBs)in sediment from a lake michigan waterway and original commercial aroclors[J].Environ Sci Technol,2013,47(15):8204-8210.
[20]HJ/T 166-2004,土壤环境监测技术规范[S].HJ/T 166-2004,The Technical Specification for soil Environmental monitoring[S](in Chinese).
[21]GB 17378.3-2007,海洋监测规范第3部分:样品采集、贮存和运输[S].GB 17378.3-2007,The specification for marine monitoring--Part 3:Sample collection,storage and transportation[S](in Chinese).
[22]史永富,林洪,黄冬梅,等.硅烷化衍生/气相色谱/电子捕获检测水产品中羟基多氯联苯的研究[J].分析测试学报,2009,28(5):568-571.SHI Y F,LIN H,HUANG D M,et al.Study on determination of hydroxylated polychlorinated biphenyls in fisher products by silylation derivatization/GC/μECD[J].Journal of Instrumental Analysis,2009,28(5):568-571(in Chinese).
[23]HONG J E,PYO H,PARK S J,et al.Determination of hydroxy metabolites of polychlorinated biphenyls in plasma and tissue by gas chromatography/mass spectrometry[J].Journal of Chromatography B,2007,856(1-2):1-8.
[24]史永富,蔡友琼,于慧娟,等.气相色谱串联质谱法用于水产品中多氯联苯二代污染物鉴别[J].分析化学,2014,42(11):1640-1645.SHI Y F,CAI Y Q,YU H J,et al.Identification of metabolized polychlorinated biphenyls in fishery products by gas chromatography tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2014,42(11):1640-1645(in Chinese).
[25]FABIAN A G,HU D F,IZABELA K K,et al.Metabolism and metabolites of polychlorinated biphenyls[J].Critical Reviews in Toxicology,2015,45(3):245-272.
[2]毕新慧,徐晓白.多氯联苯的环境行为[J].化学进展,2000,12(2):152-160.BI X H,XU X B.Behaviors of PCBs in environment[J].Process in Chemistry,2000,12(2):152-160(in Chinese).
[3]DESMET M,MOURIER B,MAHLER BJ,et al.Spatial and temporal trends in PCBs in sediment along the lower Rh8ne River,France[J].Science of the Total Environment,2012,433:189-197.
[4]NIEWIADOWSKAA,KILJANEK T,SEMENIUK S.Contamination of fish and sediments from the Vistula River by organochlorine pesticides and PCBs[J].Polish Journal of Environmental Studies,2015,24(5):2315-2320.
[5]MOORE M,MUSTAIN M,DANIEL K,et al.Antiestrogenic activity of hydroxylated polychlorinated biphenyl congeners identified in human serum[J].Toxicology and Applied Pharmacology,1997,142(1):160-168.
[6]FIELDEN M,CHENI,CHITTIM B,et al.Examination of the estrogenicity of 2,4,6,2',6'-pentachlorobiphenyl(PCB 104),its hydroxylated metabolite 2,4,6,2',6'-pentachloro-4-biphenylol(HO-PCB 104),and a further chlorinated derivative,2,4,6,2',4',6'-hexachlorobiphenyl(PCB 155)[J].Environmental Health Perspectives,1997,105(11):1238-1248.
[7]MORGADO I,HAMERS T,VEN L V,et al.Disruption of thyroid hormone binding to sea bream recombinant transthyretin by ioxinyl and polybrominated diphenyl ethers[J].Chemosphere,2007,69(1):155-163.
[8]KESTER M,BULDUK S,TIBBOEL D,et al.Potent inhibition of estrogen sulfotransferase by hydroxylated PCB metabolites:a novel pathway explaining the estrogenic activity of PCBs[J].Endocrinology,2000,141(5):1897-1900.
[9]WOODHEAD R J,LAW R J,MATTHIESSEN P.Polycyclic aromatic hydrocarbons in surface sediments around england and wales,and theirpossible biological significance[J].Marine Pollution Bulletin,1999,38(9):773-790.
[10]WINKELS H,LYCHAGIN M,MARIN G,et al.Geochronology of priority pollutants in sedimentation zones of the Volga and Danube delta in comparison with the Rhine delta[J].Applied Geochemistry,1998,13(5):581-591.
[11]WONG C S,CAPELape P D,NOWELL L H.National-scale,field-based evaluation of the biota-sediment accumulation factor model[J].Environmental Science and Technology,2001,35(9):1709-1715.
[12]GEWURTZ S B,GANDHI N,CHRISTENSEN G N,et al.Use of a food web model to evaluate the factors responsible for high PCB fish concentrations in Lake Ellasjoen,a high Arctic Lake[J].Environmental Science&Pollution Research,2009,16(2):176-190.
[13]MORRISON H,GOBAS F,LAZA R,et al.Development and verification of a benthic/pelagic food web bioaccumulation model for PCB congeners in western Lake Erie[J].Environmental Science and Technology,1997,31(11):3267-3273.
[14]LOPES C,PERGA ME,PERETTI A,et al.Is PCBs concentration variability between and within freshwater fish species explained by their contamination pathways?[J].Chemosphere,2011,85(3):502-508.
[15]WOLSKA L.Miniaturised analytical procedure of determining polycyclic aromatic hydrocarbons and polychlorinated biphenyls in bottom sediments[J].Journal of Chromatography A,2002,595(1-2):173-180.
[16]ABRAHAM VM,LYNN J.Determination of hydroxylated polychlorinated biphenyls by ion trap gas chromatography-tandem mass spectrometry[J].Journal of Chromatography A,1997,790(1):131-141.
[17]MARTINEZ A,NORSTR9M K,WANG K,et al.Polychlorinated biphenyls in the surficial sediment of Indiana Harbor and Ship Canal,Lake Michigan[J].Environment International,2010,36(8):849-854.
[18]MAREK R F,THORNE P S,WANG K,et al.PCBs and OH-PCBs in Serum from Children and Mothers in Urban and Rural U.S.Communities[J].Environ Sci Technol,2013,47(7):3353-3361.
[19]MAREK R F,MARTINEZ A,HORNBUCKLE K C.Discovery of hydroxylated polychlorinated biphenyls(OH-PCBs)in sediment from a lake michigan waterway and original commercial aroclors[J].Environ Sci Technol,2013,47(15):8204-8210.
[20]HJ/T 166-2004,土壤环境监测技术规范[S].HJ/T 166-2004,The Technical Specification for soil Environmental monitoring[S](in Chinese).
[21]GB 17378.3-2007,海洋监测规范第3部分:样品采集、贮存和运输[S].GB 17378.3-2007,The specification for marine monitoring--Part 3:Sample collection,storage and transportation[S](in Chinese).
[22]史永富,林洪,黄冬梅,等.硅烷化衍生/气相色谱/电子捕获检测水产品中羟基多氯联苯的研究[J].分析测试学报,2009,28(5):568-571.SHI Y F,LIN H,HUANG D M,et al.Study on determination of hydroxylated polychlorinated biphenyls in fisher products by silylation derivatization/GC/μECD[J].Journal of Instrumental Analysis,2009,28(5):568-571(in Chinese).
[23]HONG J E,PYO H,PARK S J,et al.Determination of hydroxy metabolites of polychlorinated biphenyls in plasma and tissue by gas chromatography/mass spectrometry[J].Journal of Chromatography B,2007,856(1-2):1-8.
[24]史永富,蔡友琼,于慧娟,等.气相色谱串联质谱法用于水产品中多氯联苯二代污染物鉴别[J].分析化学,2014,42(11):1640-1645.SHI Y F,CAI Y Q,YU H J,et al.Identification of metabolized polychlorinated biphenyls in fishery products by gas chromatography tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2014,42(11):1640-1645(in Chinese).
[25]FABIAN A G,HU D F,IZABELA K K,et al.Metabolism and metabolites of polychlorinated biphenyls[J].Critical Reviews in Toxicology,2015,45(3):245-272.