基于串联SPE净化和GC-HRMS技术测定母乳中溴代二噁英/呋喃
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摘要
[背景]溴代二噁英/呋喃(PBDD/Fs)主要来源于溴代阻燃剂的排放。随着近几十年来溴代阻燃剂的大量使用,环境中的溴代二噁英/呋喃的含量逐渐增高。[目的 ]建立快速、准确测定母乳中13种溴代二噁英/呋喃的气相-高分辨质谱(GC-HRMS)检测方法。[方法 ]将母乳冷冻干燥后,经加速溶剂萃取仪提取,分散固相萃取除脂,串联固相萃取净化和气相-高分辨质谱检测,同位素稀释法定量。[结果 ]本方法的检出限为0.002～0.012 pg/g(以50 g样品计);具有良好的线性范围,决定系数(R2)>0.99;准确度和精密度实验结果显示,低浓度和高浓度的加标回收率分别为71.8%～101.8%、80.5%～97.8%,相对标准偏差(RSD)<10%。基于本方法,测定了40份上海地区的母乳样品,PBDDs没有检出,PBDFs有2,3,7,8-四溴代二苯并呋喃(2,3,7,8-Tetra BDF)、1,2,3,4,6,7,8-七溴代二苯并呋喃(1,2,3,4,6,7,8-HpBDF)和八溴代二苯并呋喃(OBDF)共3种化合物检出,检出率分别是72.5%、100%和67.5%。[结论 ]所建方法用于测定母乳样本中PBDD/Fs,结果表明该方法快速、准确、高效、可靠,为开展PBDD/Fs暴露风险评估和毒理学研究提供了方法学支持。
[Background] The emissions of brominated flame retardants have been proved to be the major source of polybrominated dibenzo-p-dioxin/furans(PBDD/Fs). With the extensive use of brominated flame retardants in recent decades, the concentrations of PBDD/Fs in the environment increase gradually.[Objective] This study aims to establish a rapid and accurate method for the determination of 13 PBDD/F congeners in human milk by gas chromatography-high resolution mass spectrometry(GC-HRMS). [Methods] Lyophilized human milk was subject to accelerated solvent extraction, dispersive solid phase extraction(SPE) defatting, and tandem SPE purification successively, and consequently detected by GC-HRMS with isotopic dilution method. [Results] This method showed low limits of detection(LOD, 0.002-0.012 ng/g, in 50 g milk sample), good linearity(correlation coefficients, R2 > 0.99), satisfactory accuracy(the recovery rates of lowconcentration spiked standard were 71.8%-101.8%, and the recovery rates of high-concentration spiked standard were 80.5%-97.8%), and high precision(relative standard deviations, RSD < 10%). Forty breast milk samples collected in Shanghai were determined by the method. PBDDs were not detected, and three PBDF congeners including 2, 3, 7, 8-tetrabromodibenzofuran(2, 3, 7, 8-TetraBDF), 1, 2, 3, 4, 6, 7, 8-heptabromodibenzofuran(1, 2, 3, 4, 6, 7, 8-HpBDF), andoctabromodibenzofuran(OBDF) were positive, with detection rates of 72.5%, 100%, and 67.5%, respectively.[Conclusion] This method has exhibited rapidness, accuracy, efficiency, and reliability for the determination of PBDD/Fs in human milk samples. It provides methodological support for PBDD/Fs exposure risk assessment and toxicological research.
[Background] The emissions of brominated flame retardants have been proved to be the major source of polybrominated dibenzo-p-dioxin/furans(PBDD/Fs). With the extensive use of brominated flame retardants in recent decades, the concentrations of PBDD/Fs in the environment increase gradually.[Objective] This study aims to establish a rapid and accurate method for the determination of 13 PBDD/F congeners in human milk by gas chromatography-high resolution mass spectrometry(GC-HRMS). [Methods] Lyophilized human milk was subject to accelerated solvent extraction, dispersive solid phase extraction(SPE) defatting, and tandem SPE purification successively, and consequently detected by GC-HRMS with isotopic dilution method. [Results] This method showed low limits of detection(LOD, 0.002-0.012 ng/g, in 50 g milk sample), good linearity(correlation coefficients, R2 > 0.99), satisfactory accuracy(the recovery rates of lowconcentration spiked standard were 71.8%-101.8%, and the recovery rates of high-concentration spiked standard were 80.5%-97.8%), and high precision(relative standard deviations, RSD < 10%). Forty breast milk samples collected in Shanghai were determined by the method. PBDDs were not detected, and three PBDF congeners including 2, 3, 7, 8-tetrabromodibenzofuran(2, 3, 7, 8-TetraBDF), 1, 2, 3, 4, 6, 7, 8-heptabromodibenzofuran(1, 2, 3, 4, 6, 7, 8-HpBDF), andoctabromodibenzofuran(OBDF) were positive, with detection rates of 72.5%, 100%, and 67.5%, respectively.[Conclusion] This method has exhibited rapidness, accuracy, efficiency, and reliability for the determination of PBDD/Fs in human milk samples. It provides methodological support for PBDD/Fs exposure risk assessment and toxicological research.
引文
[1]PISKORSKA-PLISZCZY?SKA J,MASZEWSKI S. Brominated dioxins:little-known new health hazards-a review[J].Bull Vet Inst Pulawy,2014,58(3):327-335.
[2]SAKAI S I,WATANABE J,HONDA Y,et al. Combustion of brominated flame retardants and behavior of its byproducts[J]. Chemosphere,2001,42(5/7):519-531.
[3]ZHANG M,BUEKENS A,LI X. Brominated flame retardants andtheformationofdioxinsandfuransinfiresand combustion[J]. J Hazard Mater,2016,304:26-39.
[4]HAYAKAWAK,TAKATSUKIH,WATANABEI,etal.Polybrominated diphenyl ethers(PBDEs),polybrominated dibenzo-p-dioxins/dibenzofurans(PBDD/Fs)and monobromo-polychlorinateddibenzo-p-dioxins/dibenzofurans(MoBPXDD/Fs)in the atmosphere and bulk deposition in Kyoto,Japan[J]. Chemosphere,2004,57(5):343-356.
[5]LI H,FENG J,SHENG G,et al. The PCDD/F and PBDD/F pollution in the ambient atmosphere of Shanghai,China[J].Chemosphere,2008,70(4):576-583.
[6]LI H,YU L,SHENG G,et al. Severe PCDD/F and PBDD/F pollution in air around an electronic waste dismantling area in China[J]. Environ Sci Technol,2007,41(16):5641-5646.
[7]LI H,ZHOU L,MO L,et al. Levels and congener profiles of particle-bound polybrominated dibenzo-p-dioxins/furans(PBDD/Fs)in ambient air around Guangzhou,China[J].Bull Environ Contam Toxicol,2011,87(2):184-189.
[8]SHY C G,HUANG H L,CHAO H R,et al. Cord blood levels of thyroidhormonesandIGF-1weaklycorrelatewithbreast milk levels of PBDEs in Taiwan[J]. Int J Hyg Environ Health,2012,215(3):345-351.
[9]RAWN D F,SADLER A R,CASEY V A,et al. Dioxins/furans and PCBs in Canadian human milk:2008-2011[J]. Sci Total Environ,2017,595:269-278.
[10]CHEN M W,CASTILLO B A,LIN D Y,et al. Levels of PCDD/Fs,PBDEs,and PBDD/Fs in breast milk from southern Taiwan[J]. Bull Environ Contam Toxicol,2018,100(3):369-375.
[11]ZHANG L,YIN S,LI J,et al. Increase of polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinatedbiphenylsinhumanmilkfromChinain2007-2011[J]. Int J Hyg Environ Health,2016,219(8):843-849.
[12]DENG B,ZHANG J,ZHANG L,et al. Levels and profiles of PCDD/Fs,PCBs in mothers’ milk in Shenzhen of China:estimationofbreast-fedinfants’intakes[J].EnvironInt,2012,42:47-52.
[13]LIN Y,FENG C,XU Q,et al. A validated method for rapid determination of dibenzo-p-dioxins/furans(PCDD/Fs),polybrominateddiphenylethers(PBDEs)and polychlorinated biphenyls(PCBs)in human milk:focus on utility of tandem solid phase extraction(SPE)cleanup[J].Anal Bioanal Chem,2016,408(18):4897-4906.
[14]FERNANDES A R,ROSE M,MORTIMER D,et al. Mixed brominated/chlorinated dibenzo-p-dioxins,dibenzofuransa ndbiphenyls:simultaneou scongener-selective determinationinfood[J].JChromatogrA,2011,1218(51):9279-9287.
[15]CROES K,COLLES A,KOPPEN G,et al. Determination of PCDD/Fs,PBDD/Fs and dioxin-like PCBs in human milk from mothers residing in the rural areas in Flanders,using the CALUXbioassayandGC-HRMS[J].Talanta,2013,113:99-105.
[16]Tetra-through octa-chlorinateddioxins and furans by isotope dilution HRGC/HRMS:Method 1613[S]. Washington DC:US Environmental Protection Agency,1994.
[17]LU D,LIN Y,FENG C,et al. Levels of polychlorinated dibenzo-p-dioxins/furans(PCDD/Fs)and dioxin-like polychlorinatedbiphenyls(DL-PCBs)inbreastmilk inShanghai,China:atemporalupwardtrend[J].Chemosphere,2015,137:14-24.
[18]LU D,LIN Y,FENG C,et al. Determination of polybrominated diphenyl ethers and polychlorinated biphenyls in fishery and aquaculture products using sequential solid phase extraction and large volume injection gas chromatography/tandem mass spectrometry[J]. J Chromatogr B,2014,945-946:75-83.
[19]WASSER J,BERMAN T,LERNER-GEVA L,et al. Biological monitoring of persistent organic pollutants in human milk in Israel[J]. Chemosphere,2015,137:185-191.
[20]PRATT I,ANDERSON W,CROWLEY D,et al. Brominated and fluorinated organic pollutants in the breast milk of first-time Irish mothers:is there a relationship to levels in food?[J].Food Addit Contam,2013,30(10):1788-1798.
[2]SAKAI S I,WATANABE J,HONDA Y,et al. Combustion of brominated flame retardants and behavior of its byproducts[J]. Chemosphere,2001,42(5/7):519-531.
[3]ZHANG M,BUEKENS A,LI X. Brominated flame retardants andtheformationofdioxinsandfuransinfiresand combustion[J]. J Hazard Mater,2016,304:26-39.
[4]HAYAKAWAK,TAKATSUKIH,WATANABEI,etal.Polybrominated diphenyl ethers(PBDEs),polybrominated dibenzo-p-dioxins/dibenzofurans(PBDD/Fs)and monobromo-polychlorinateddibenzo-p-dioxins/dibenzofurans(MoBPXDD/Fs)in the atmosphere and bulk deposition in Kyoto,Japan[J]. Chemosphere,2004,57(5):343-356.
[5]LI H,FENG J,SHENG G,et al. The PCDD/F and PBDD/F pollution in the ambient atmosphere of Shanghai,China[J].Chemosphere,2008,70(4):576-583.
[6]LI H,YU L,SHENG G,et al. Severe PCDD/F and PBDD/F pollution in air around an electronic waste dismantling area in China[J]. Environ Sci Technol,2007,41(16):5641-5646.
[7]LI H,ZHOU L,MO L,et al. Levels and congener profiles of particle-bound polybrominated dibenzo-p-dioxins/furans(PBDD/Fs)in ambient air around Guangzhou,China[J].Bull Environ Contam Toxicol,2011,87(2):184-189.
[8]SHY C G,HUANG H L,CHAO H R,et al. Cord blood levels of thyroidhormonesandIGF-1weaklycorrelatewithbreast milk levels of PBDEs in Taiwan[J]. Int J Hyg Environ Health,2012,215(3):345-351.
[9]RAWN D F,SADLER A R,CASEY V A,et al. Dioxins/furans and PCBs in Canadian human milk:2008-2011[J]. Sci Total Environ,2017,595:269-278.
[10]CHEN M W,CASTILLO B A,LIN D Y,et al. Levels of PCDD/Fs,PBDEs,and PBDD/Fs in breast milk from southern Taiwan[J]. Bull Environ Contam Toxicol,2018,100(3):369-375.
[11]ZHANG L,YIN S,LI J,et al. Increase of polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinatedbiphenylsinhumanmilkfromChinain2007-2011[J]. Int J Hyg Environ Health,2016,219(8):843-849.
[12]DENG B,ZHANG J,ZHANG L,et al. Levels and profiles of PCDD/Fs,PCBs in mothers’ milk in Shenzhen of China:estimationofbreast-fedinfants’intakes[J].EnvironInt,2012,42:47-52.
[13]LIN Y,FENG C,XU Q,et al. A validated method for rapid determination of dibenzo-p-dioxins/furans(PCDD/Fs),polybrominateddiphenylethers(PBDEs)and polychlorinated biphenyls(PCBs)in human milk:focus on utility of tandem solid phase extraction(SPE)cleanup[J].Anal Bioanal Chem,2016,408(18):4897-4906.
[14]FERNANDES A R,ROSE M,MORTIMER D,et al. Mixed brominated/chlorinated dibenzo-p-dioxins,dibenzofuransa ndbiphenyls:simultaneou scongener-selective determinationinfood[J].JChromatogrA,2011,1218(51):9279-9287.
[15]CROES K,COLLES A,KOPPEN G,et al. Determination of PCDD/Fs,PBDD/Fs and dioxin-like PCBs in human milk from mothers residing in the rural areas in Flanders,using the CALUXbioassayandGC-HRMS[J].Talanta,2013,113:99-105.
[16]Tetra-through octa-chlorinateddioxins and furans by isotope dilution HRGC/HRMS:Method 1613[S]. Washington DC:US Environmental Protection Agency,1994.
[17]LU D,LIN Y,FENG C,et al. Levels of polychlorinated dibenzo-p-dioxins/furans(PCDD/Fs)and dioxin-like polychlorinatedbiphenyls(DL-PCBs)inbreastmilk inShanghai,China:atemporalupwardtrend[J].Chemosphere,2015,137:14-24.
[18]LU D,LIN Y,FENG C,et al. Determination of polybrominated diphenyl ethers and polychlorinated biphenyls in fishery and aquaculture products using sequential solid phase extraction and large volume injection gas chromatography/tandem mass spectrometry[J]. J Chromatogr B,2014,945-946:75-83.
[19]WASSER J,BERMAN T,LERNER-GEVA L,et al. Biological monitoring of persistent organic pollutants in human milk in Israel[J]. Chemosphere,2015,137:185-191.
[20]PRATT I,ANDERSON W,CROWLEY D,et al. Brominated and fluorinated organic pollutants in the breast milk of first-time Irish mothers:is there a relationship to levels in food?[J].Food Addit Contam,2013,30(10):1788-1798.