气相色谱-电子轰击源质谱测定海产品中多溴联苯（醚）

海产品中多溴联苯残留现在已经成为新的食品安全危害因子,但是针对海产品中多溴联苯检测方法的研究还不多。针对海产品基质的特殊性,研究建立了样品的加速溶剂萃取仪（ASE）提取、多层硅胶层析柱净化前处理方法,采用定性离子和外标定量法建立了气相色谱-电子轰击源质谱（GC-EI/MS）法检测海产品中多溴联苯（PBBs）和多溴联苯醚（PBDEs）的定性和定量方法。所建立的十三种多溴联苯和多溴联苯醚GC-EI/MS方法的线性范围在10～200ng/mL,检出限在0.44～6.0ng/mL之间,具有较宽的线性范围和很高的灵敏度。通过添加回收实验表明,方法回收率在59.7%～97.2%之间,相对标准偏差（RSD）在1.0%～13.7%之间。      

QuEChERS-气相色谱-串联质谱法测定蔬菜中多溴联苯和多溴联苯醚

建立QuEChERS-气相色谱-串联质谱法测定蔬菜中20种多溴联苯和多溴联苯醚残留量方法。样品采用酸化乙腈振荡提取,无水硫酸镁与氯化钠盐析,经十八烷基硅烷键合硅胶和乙二胺-N-丙基硅烷净化,并利用气相色谱-串联质谱在选择反应监测模式下进行检测,外标法定量。1~6溴代联苯及联苯醚的线性范围为0.05~5.0 mg/L、7~8溴代联苯及联苯醚为0.1~5.0 mg/L、9~10溴代联苯和联苯醚为0.2~5.0 mg/L;相关系数(r)均大于0.99,方法检出限范围为0.30~17.67 ng/kg。在3种不同蔬菜基质中3个添加水平(0.25、0.5、2.5 mg/kg)的平均回收率为70.5%~118.9%,相对标准偏差为1.3%~11.2%。该方法前处理简单快速、灵敏度高,具有良好的回收率和稳定性,适用于蔬菜中多种多溴联苯和多溴联苯醚残留量的测定与确证。     

气相色谱-质谱法测定水中多溴联苯醚残留量

建立一套准确、高效、快捷的水中多溴联苯醚（polybrominated diphenyl ethers,PBDEs）残留量的检测方法。样品采用二氯甲烷提取,氮吹浓缩,正己烷定容,然后以气相色谱-质谱测定。19 种PBDEs组分线性良好,相关系数R2均大于0.99,相对标准偏差（relative standard deviation,RSD）（n=6）为1.5%～5.6%,检出限为0.1～1.0 μg/L。PBDE-3和PBDE-209平均加标回收率为84.3%～93.2%,RSD为3.6%～10.1%。结果表明,该方法各项指标均能满足检测工作要求,适用于水中PBDEs残留量的日常检测。     

气相色谱-串联质谱法测定蔬菜中8种多溴联苯醚

目的 建立气相色谱-串联质谱法测定蔬菜中8种多溴联苯醚方法。方法 样品采用正己烷：丙酮（V:V,1:1）提取,用25 mg N-丙基乙二胺(primary secondary amine, PSA)、150 mg MgSO4净化,利用气相色谱-串联质谱在多反应离子监测模式下进行检测,外标法定量。结果8种溴代阻燃剂的相关系数（r）均大于0.99,方法检出限范围为0.0001-0.0009 mg/kg。在3 种不同蔬菜基质中3 个添加水平（0.005、0.02、0.2 mg/kg）的平均回收率为91.1～114%,相对标准偏差为1.7%～8.7%。结论 该方法前处理简单快速、灵敏度高,具有良好的回收率和稳定性,适用于不同种蔬菜中8种多溴联苯醚的测定。     

气相色谱测定小麦和稻米中11种多溴联苯醚

目的 建立气相色谱-电子捕获检测器法测定小麦和稻米中11种代表性多溴联苯醚的分析方法。方法 小麦粉或糙米粉经水化后,采用乙酸乙酯提取和5 g酸性硅胶(44%, m:m)固相净化柱净化,使用气相色谱-电子捕获检测器进行检测,外标法定量。结果 小麦和稻米中,11种多溴联苯醚的定量线性范围分别为0.1~50.0 ng/g,0.2~50 ng/g,0.5~50 ng/g,回归系数均大于0.998;方法检出限在0.03~0.15 ng/g之间,定量限为0.1~0.5 ng/g之间;方法回收率为66.9%~93.5%,相对标准偏差为0.4%~17.8%。结论 本方法的样品前处理简单,对仪器要求低,准确度和精密度较好,适用于小麦和稻米中多溴联苯醚的检测分析。     

GC-MS/MS同时测定鱼样中39种多溴联苯醚

目的采用快速溶剂萃取(ASE)、系列固相萃取[SPE,包括分散性固相萃取(D-SPE)和串联SPE柱]和GC-MS/MS,建立一个便捷、高效测定鱼样中39种多溴联苯醚(PBDEs)的检测方法。方法代表性鲈鱼样品(脂肪含量11%)经冷冻干燥后ASE提取,然后采用D-SPE去除脂肪和串联SPE柱净化,最后采用GC-MS/MS检测,同位素内标法定量。结果本方法的检测限(MDLs)为0.16～3.29pg/g;具有良好的线性范围(R2>0.998)、准确度(除BDE30为53%以外,其他组分回收率为62%～139%)和精密度(RSD<20%);测定参考物质的结果均在标准值范围内,与气相色谱磁场电场双聚焦高分辨质谱(GC-HRMS)测定结果一致。结论本方法为鱼样中PBDEs检测提供了一个快速、简便和可靠的方法,以便于日常监测和评估鱼中残留PBDEs对人体健康风险的研究。     

GCMS/MS 同时测定鱼样中39 种多溴联苯醚

目的 采用快速溶剂萃取(ASE)、系列固相萃取(SPE, 包括分散性固相萃取(DSPE)和串联SPE柱)和GCMS/MS, 建立一个便捷、高效测定鱼样中39种多溴联苯醚(PBDEs)的检测方法。方法 代表性鲈鱼样品(脂肪含量11%)经冷冻干燥后ASE提取, 然后采用DSPE去除脂肪和串联SPE柱净化, 最后采用GCMS/MS检测, 同位素内标法定量。结果 本方法的检测限(MDLs)为0.16~3.29 pg/g; 具有良好的线性范围(R2>0.998)、准确度(除BDE30为53%以外, 其他组分回收率为62%~1139%)和精密度(RSD<20%); 测定参考物质的结果均在标准值范围内, 与气相色谱磁场电场双聚焦高分辨质谱(GC/HRMS)测定结果一致。结论 本方法为鱼样中PBDEs检测提供了一个快速、简便和可靠的方法, 适用于对痕量PBDEs残留水平的食用鱼进行人体健康风险评价研究。     

气相色谱-串接质谱法检测乳制品中持久性有机污染物多溴联苯醚同系物的研究

研究建立了乳制品中PBDEs的气相色谱-串接质谱法分析检测方法,并优化了其色谱、质谱条件;确定有效的样品前处理步骤;基质加标回收率大于85％;各组分在0．1～1μg·mL-1线性范围内具有良好的线性关系,相关系数均大于0．99,检测限范围0．001—0．02μg·mL-1之间。     

使用气质联用法分析电子烟烟液及气溶胶中20种多溴联苯和多溴联苯醚

建立一种测定电子烟烟液及气溶胶中20种多溴联苯和多溴联苯醚的方法。样品采用纯水和正己烷（体积比2∶1）提取后氮吹浓缩,再使用气质联用仪进行检测,内标法定量。本方法的线性范围为0.01 mg/L～1.0mg/L,方法检出限范围为0.88 ng/g～7.97 ng/g,在3个添加水平的回收率分别为81.6%～117.8%,相对标准偏差为2.7%～9.8%。应用本方法对市售的10个电子烟气溶胶样品及8个电子烟烟液样品进行分析,均未检出有多溴联苯及多溴联苯醚。     

食品中多溴联苯醚及其羟基衍生物的研究进展

近年来,由于多溴联苯醚及其羟基衍生物具有毒性和污染持久性,它们的研究越来越受到重视。本文以食品中多溴联苯醚及其羟基衍生物为重点,对多溴联苯醚及其羟基衍生物的性质、主要来源、毒性、以及在食品中的污染水平和分析方法等进行了评述,为我国开展食品领域内多溴联苯醚及其羟基衍生物的限量制定和研究提供参考。      

固相萃取-超高效液相色谱-电喷雾离子源-串联质谱法测定人血中羟基化多溴联苯醚

目的建立了固相萃取(SPE)柱萃取和净化、超高效液相色谱-电喷雾离子源-串联质谱(UPLC-ESI--MS/MS)检测血液中11种羟基多溴联苯醚(OH-PBDEs)的方法。方法对流动相和SPE萃取条件进行了优化。结果人血液加标回收率53.2%～117.9%,相对标准偏差4.71%～18.85%,检出限0.008 86～0.058 9 ng/ml。结论本方法不需要衍生化,灵敏度高、准确度和精密度好,简便快速,溶剂消耗量少,适用于人血样品中羟基多溴联苯醚的测定。     

Electron impact and electron capture negative ionization mass spectra of polybrominated diphenyl ethers and methoxylated polybrominated diphenyl ethers

This review presents the electron impact (EI) and electron capture negative ionization (ECNI) mass spectra of the polybrominated diphenyl ether (PBDE) flame retardants and of their methoxy derivatives. Data from the literature are reviewed, and full spectra from our laboratory are reported to correct some of the errors that have crept into some previously published data. The EI spectra of the PBDEs are dominated by molecular ions and by singly and doubly charged ions due to the loss of Br2 from the molecular ion. The ECNI spectra of PBDEs with seven or less bromines are dominated by Br(-) and by HBr2(-); the spectra of those with eight or more bromines are dominated bytetra- or pentabromophenoxide ions due to cleavage of the phenyl-ether linkage. The EI mass spectra of methoxy-PBDEs can easily distinguish the position of the methoxy group relative to the phenyl-ether linkage. The ECNI spectra of these compounds are also dominated by Br(-) and HBr2(-). In both ionization modes and for both compound groups, there are some subtle features, which often allow one to rule in or out substitution at one or more of the ortho-ring positions.     

Evaluating daily exposure to polychlorinated biphenyls and polybrominated diphenyl ethers in fish oil supplements

Fish oil supplements have become a popular means of increasing one's dietary intake of essential polyunsaturated fatty acids. However, there is growing concern that the levels and potential health effects of lipophilic organic contaminants such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) may diminish some of the health benefits associated with the daily consumption of fish oil supplements. In this study, ten over-the-counter fish oil supplements available in the United States were analysed for PCBs and PBDEs and daily exposures calculated. Based on manufacturers’ recommended dosages, daily intakes of PCBs and PBDEs ranged from 5 to 686 ng day^?1 and from 1 to 13 ng day^?1, respectively. Daily consumption of fish oil supplements expose consumers to PCBs and PBDEs. However, in comparison with fish ingestion, fish supplements may decrease daily PCB exposure and provide a safer pathway for individuals seeking to maintain daily recommended levels of polyunsaturated fatty acids.     

索氏提取-气相色谱/质谱法测定食品包装材料中羟基苯醚

目的 建立一种适用于食品包装材料中羟基苯醚的气相色谱/质谱检测方法。方法 采用索氏提取法, 以二丙醚萃取提取样品中二苯醚类物质, 经色谱分离后采用质谱检测器, 保留时间、分子碎片峰定性, 外标法定量。结果 对于二苯醚类物质检测回收率范围88%~109%, 相对标准偏差<3.9, 检测限0.032 ~0.067mg/L。结论 本方法便捷、重现性好, 适用于各种类型食品包装材料中二苯醚类物质检测。     

Development and application of a simplified clean-up procedure for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in horse fat by gas chromatography-tandem mass spectrometry (GC-MS/MS)

A simplified clean-up procedure was developed in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS) for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in adipose tissue. Clean-up was performed by the successive application of a Mega Bond Elut® silica column and a Bond Elut® PCB column. Validation of the method was conducted according to European Union Commission Decision 2002/657/EC. In order to evaluate the applicability of the method, 44 horse fat samples were analysed. The total PCB concentration (sum of PCBs 28, 52, 101, 118, 138, 153 and 180) ranged from 5.35 to 140 ng g^-1 lipid weight. The total PBDE concentration (sum of BDEs 28, 47, 99, 100, 153, 154 and 183) ranged from below the decision limit to 6.34 ng g^-1 lipid weight.     

Rapid determination of polybrominated diphenyl ethers (PBDEs) in fish using selective pressurized liquid extraction (SPLE) combined with automated online gel permeation chromatography-gas chromatography mass spectrometry (GPC-GC/MS)

A rapid method for the determination of seven predominant polybrominated diphenyl ethers (PBDEs) in fish was developed. The analysis could be completed in 1 h. The PBDEs in the sample were extracted with fat by selective pressurized liquid extraction (SPLE) using acid alumina as a fat retainer. After concentration, the extract was directly injected into online gel permeation chromatography with gas chromatography-mass spectrometry (GPC-GC/MS) in negative chemical ionization (NCI) mode. Method detection limits of seven PBDEs were between 0.002 and 0.005 ng g^?1 fat. Quantitative recoveries ranging from 81.9% to 110.3% were obtained by analysis of spiked fish. The relative standard deviations were less than 15% (n = 6). The method was applied to a certified reference material of fish; all results were in the reference ranges. It was shown to be a rapid and reliable alternative in the routine analysis for PBDEs.     

防虫蛀纯羊毛绒线中Permethrin残留量的GC/MS测定

毛绒织物样品以1：1丙酮－正己烷混合溶剂超声提取后，提取液经Celite层析柱净化，40℃旋转蒸发浓缩、定容，由色－质联用仪测定试样中的氯菊酯（Permethrin)含量。本方法对目标化合物的检测限量在0．1－0．5mg/kg范围内，平均回收率介于89．1％－101．2％之间，相对标准偏差为2．3％－4．4％。