气相色谱-质谱联用检测塑料产品中溴化阻燃剂

建立了气相色谱-质谱联用测定塑料产品中多溴联苯和多溴联苯醚的方法.以甲苯为提取溶剂,超声提取电子电气产品中多溴联苯(PBBs)和多溴联苯醚 (PBDEs),采用气相色谱-质谱法(GC-MS)检测.SCAN和SIM同时扫描,采用质谱特征离子定量分析.结果表明: 9种多溴联苯(PBBs)和10种多溴联苯醚(PBDEs)的线性关系、检出限、回收率和精密度都较好,RSD均<5.0%,PBBs回收率在97%～111%之间;PBDEs回收率在82%～115%之间.本方法前处理简便,灵敏度高,定性、定量分析准确可靠,且分析时间短,适用于塑料产品中PBBs和PBDEs的测定.     

热解析-裂解-气相色谱/质谱联用法测定电子电气产品中的多溴二苯醚

建立了热解析-裂解-气相色谱/质谱法测定电子电气中多溴二苯醚(PBDEs)的方法。采用气相色谱-质谱总离子流和选择离子流对PBDEs进行定性和定量测定。对热解析温度,热解析时间,热解析升温速率和附件初始温度进行了优化,并进行了线性关系、精密度等试验。本方法线性范围200~1000 mg/kg,相关系数为0.995,检出限为50 mg/kg,相对标准偏差小于15%。本方法可直接固体进样,简化了前处理步骤,适用于电子电气产品中PBDEs的测定,满足欧盟Ro HS指令限量的检测要求。     

QuEChERS—气相色谱—串联质谱测定食品中的多溴联苯和多溴二苯醚类阻燃剂

建立了QuEChERS-气相色谱-串联质谱(GC-MS/MS)法测定食品的多溴联苯和多溴二苯醚类物质。采用正己烷或乙腈提取并浓缩目标物后，用无水MgSO₄、乙二胺-N-丙基硅烷(PSA)和十八烷基硅烷键合硅胶(C18)净化，以DB-5HT色谱柱(15 m×0.25 mm×0.1μm)进行分离，质谱采用电子轰击电离源，在多反应监测模式下进行检测，外标法定量。实验优化了提取条件，比较了提取溶剂的种类和体积、酸的体积对检测结果的影响。结果表明，12种多溴联苯和13种多溴二苯醚共25种目标物均呈现良好线性关系，相关系数(r²)≥0.999,方法的检出限为3～180μg/kg,定量限为10～600μg/kg,平均加标回收率为60.23%～106.97%,相对标准偏差(RSDs,n=6)为0.20%～11.96%。该测定方法操作简单，灵敏度高，适用于食品中多溴联苯和多溴二苯醚类物质的高效分析检出。     

高效液相色谱法测定电子电气产品中多溴联苯和多溴联苯醚

提出了高效液相色谱法测定电子电气产品中多溴联苯和多溴联苯醚含量的方法。普通塑料样品采用正己烷-丙酮(1+1)混合溶液作为提取溶剂进行微波萃取,含金属的塑料样品采用乙酸乙酯作为提取溶剂进行超声波萃取,提取液采用NUCLEODUR Sphinx RP C18色谱柱为分离柱分离,以不同体积比混合的水和乙腈为流动相进行梯度洗脱,检测波长为226nm。多溴联苯和多溴联苯醚的质量浓度在0.2～50mg.L-1范围内与峰面积呈线性关系,测定下限(10S/N)在2.3～5.0mg.kg-1之间。     

微波辅助萃取/气相色谱-质谱法对电子电气产品中多溴二苯醚的测定

建立了微波辅助萃取/气相色谱-质谱测定电子电气产品中多溴二苯醚(PBDEs)含量的方法,优化了萃取溶剂、萃取温度、萃取时间等微波萃取条件和GC-MS仪器分析条件.方法的准确度和重复性满足定量分析的要求,12种PBDEs组分的定量下限为0.27 ～4.3 mg/kg.将该方法用于分析6种电子电气样品,PBDEs的含量为0.3 ～1.7×104 mg/kg.该方法简单、快速、有机溶剂用量少,满足RoHS指令的要求和实际产品检测的需要 .     

微波辅助萃取-气相色谱质谱法检测生物体内的多溴联苯醚

建立了微波辅助萃取-气相色谱质谱法测定生物样品中的多溴联苯醚(PBDEs)的方法,优化了萃取剂的种类、萃取剂用量、萃取时间等微波萃取条件和GC-MS仪器分析条件。正己烷-丙酮混合溶剂提取后,经实验室自制的多层硅胶柱分离纯化,用气相色谱-质谱进行测定,该方法基质加标回收率在60%～77%之间,相对标准偏差在11%～18%之间,方法的检测限为0.03～0.20ng/g,适用于生物样品中PBDEs的测定。     

电子电气产品中多溴联苯和多溴二苯醚的高效液相色谱/串联质谱法测定

样品经超声提取后,用液相色谱-串联质谱法分析,采用同位素质量数定性,外标法定量。本法对五溴联苯(5-PBB)、八溴联苯(8-PBB)、十溴联苯(10-PBB)、五溴二苯醚(5-PBDE)、八溴二苯醚(8-PBDE)、十溴二苯醚(10-PBDE)定量限为50 mg.kg-1;对以上六种多溴联苯、多溴二苯醚分别添加50 mg.kg-1、100 mg.kg-1、150 mg.kg-1并进行10次测定的回收率为85.5%～107%;精密度为1.10%～6.60%;采用标准品加入法对塑料、橡胶的空白样品分别添加5-PBB、8-PBB、10-PBB、5-PBDE、8-PBDE、10-PBDE各0 mg.kg-15、0 mg.kg-1、100 mg.kg-1、150 mg.kg-1、200 mg.kg-1,并进行测定,得到线性相关系数在0.9963～0.9995。     

凝胶渗透色谱-分散固相萃取法同时测定鸡蛋中多溴联苯醚及其衍生物、四溴双酚A和六溴环十二烷

建立了一种同时检测鸡蛋中四溴双酚A(TBBP A)、六溴环十二烷(HBCD)和多溴联苯醚(PBDEs)及其衍生物羟基多溴联苯醚(OH-PBDEs)和甲氧基多溴联苯醚(MeO-PBDEs)的凝胶渗透色谱(GPC)-分散固相萃取(DSPE)-液相色谱-串联质谱(HPLC-MS/MS)和气相色谱-负化学源质谱(GC-NCI/MS)的检测方法。样品经正己烷、二氯甲烷(1∶1,V/V)加速溶剂萃取,凝胶渗透色谱净化后,经100 mg十八烷基键合硅胶(C18)分散固相萃取吸附剂去除杂质,液相色谱-串联质谱和气相色谱-负化学源质谱方法测定,外标法定量。在蛋白和蛋黄样品中添加1.0或5.0μg/kg的目标物,其回收率分别为64.5%~97.2%和65.6%~109.2%(除BDE-85为54.8%,OH-BDE-137为47.4%外),相对标准偏差小于20.2%,定量限为0.01~0.2μg/kg。     

气相色谱法测定牡蛎中多溴联苯醚

利用气相色谱-电子捕获检测器(GC-ECD),建立了牡蛎中11种多溴联苯醚(PBDEs)同时测定方法。优化了气相法与质谱联用法仪器条件,考察了不同提取溶液、固相萃取柱、净化方式等前处理条件对提取和净化效果的影响。结果表明,GC-ECD对高溴组分更灵敏;牡蛎加标样品经正己烷-二氯甲烷(1:1,V/V)提取,弗洛里硅土柱-浓硫酸净化,GC-ECD测定,PBDEs各组分标准曲线线性良好(r 0. 998),二至九溴联苯醚和十溴联苯醚方法检出限分别为0. 05 ng/g和0. 1 ng/g,回收率范围为80. 3%～104%,相对标准偏差范围为3. 0%～12%。方法可用于牡蛎中二至十溴联苯醚同时检测。     

气相色谱-质谱法测定人血清中多溴联苯

建立了血清中8种多溴联苯(PBBs,包括BB-15、18、52、101、153、180、194和206)的气相色谱-质谱检测方法。采用Oasis HLB固相萃取柱对血清样品中的多溴联苯进行萃取和初步净化,再使用自制的硅胶/酸化硅胶固相萃取柱(Sep-Pak silica/acidified silica)进行进一步的净化,并以正己烷为洗脱溶剂洗脱,氮吹洗脱液浓缩至100 μL后上样分析。以DB-5ms色谱柱(15 m×0.25 mm×0.1 μm)分离样品,在选择离子监测(SIM)模式下进行质谱检测,使用同位素内标法对8种目标物进行准确定量。结果显示,8种多溴联苯单体的方法检出限(LOD,以3.14倍标准偏差计)为0.002～0.029 ng/mL,方法定量限(LOQ,以10倍标准偏差计)为0.008～0.092 ng/mL;低、中、高3个加标水平的平均回收率为74.24%～119.49%,相对标准偏差(RSD)为1.23%～12.02%。采用本方法测定标准参考物质SRM1957和SRM1958中的BB-153含量,结果在参考值范围内。本方法准确、灵敏、操作简便,适用于血清中多溴联苯的测定。     

A Novel Sample Pretreatment Method for the Analysis of Polybrominated Diphenyl Ethers in Polymers of Waste Electrical and Electronic Equipment(WEEE)

A fast sample pretreatment method was developed to determine polybrominated diphenyl ethers (PBDEs) in polymers from waste electrical and electronic equipment (WEEE). Polymers were firstly prepared into "polymer film" to facilitate a complete Soxtec extraction. Then, three extraction parameters (including hot plate temperature, boiling time, and rinsing time) were optimized based on the recovery of target in reference polymer samples. The proposed method was successfully applied to the analysis of PBDEs in standard plastic materials from WEEE and the extraction yields of PBDEs ranged from 78.9% to 91.3%. The detection limits of PBDEs were 0.05–0.10 µg/g, indicating this method can be used as a quality assurance and quality control procedure of PBDEs in the production of electrical and electronic equipment.     

气相色谱质谱法分析土壤中多溴联苯和多溴联苯醚类化合物

建立了气相色谱-质谱法(GC-MS)分析土壤中的18种多溴联苯(PBBs)和多溴联苯醚类(PBDEs)化合物的方法.利用快速溶剂萃取(ASE)技术和凝胶净化系统(GPC)进行土壤样品的前处理,(13)C标记物作为进样内标和替代标,采用电子轰击源气相色谱质谱法(GC-EI/MS )分析-溴至七溴代PBBs和PBDEs,负...     

Fractionation of chlorinated and brominated persistent organic pollutants in several food samples by pyrenyl-silica liquid chromatography prior to GC-MS determination

A high-performance liquid chromatography (HPLC) method using a column of 2-(1-pyrenyl) ethyldimethylsilylated silica was developed in this work in order to achieve satisfactory and reproducible fractionation of polychlorinated biphenyls (PCBs) from brominated flame retardants (BFRs) (polybrominated diphenylethers, PBDEs; and polybrominated biphenyls, PBBs). After the study of different chromatographic parameters (mobile phase composition and separation temperature were the most important) an isocratic elution with isooctane:toluene (98:2, v/v) at a flow-rate of 1 mL/min, a temperature of 45 °C, and UV-detection at 225 nm was selected for fractionation of PCBs (time region, 4.0-5.8 min) from PBDEs (5.8-9.0 min) and from PBBs (5.8-11.0 min). The applicability of this method to food samples was demonstrated by fractionating PCBs from PBDEs in three food samples (cheese, milk, and fish). Interferences from PCBs (present in real samples at much higher concentrations than PBDEs) were removed in this way. In addition, by analysing these samples by gas chromatography-mass spectrometry (GC-MS) with and without previous fractionation we were able to observe an improvement in detection sensitivity for PBDEs after HPLC fractionation.     

Gas chromatography/ion trap mass spectrometry applied for the determination of polybrominated diphenyl ethers in soil

A gas chromatography/ion trap mass spectrometry (GC/ITMS) method was developed for the determination of polybrominated diphenyl ethers (PBDEs). ITMS parameters were optimized in order to achieve the best sensitivity for the PBDE analysis. Tandem mass spectrometry, along with an isotope dilution internal standard method, was used for the quantitation. Chromatographic windows were developed for mono- to hepta-BDEs, depending on the retention times when a 30-m GC column was used. A different 15-m column was used to analyze deca-BDE. Environmental soil samples collected from an electronic waste recycling site were prepared by using Soxhlet extraction and column chromatographic cleanup. Average recoveries of 61-118% were obtained for the 13C-labeled PBDE internal standards spiked in the samples prior to sample preparation. The accuracy represented by relative analytical errors was -24% to 18%, and the precision (relative standard deviation) was 11-26% (n=8). The method detection limits ranged from 0.013-0.25 ng/g for the PBDEs in soil.     

气相色谱/离子阱串联质谱法检测大气中的多溴二苯醚

运用气相色谱-离子阱质谱(ion trap mass spectrometry,ITMS)建立了大气中8种多溴二苯醚的二级质谱(MS/MS)检测方法。优化后的MS/MS方法对7种三溴至七溴二苯醚(BDE28、-47、-99、-100、-153、-154、-183)和十溴二苯醚(BDE209)的仪器检出限分别为0.04~0.23 pg和9.38 pg;方法检出限为6.0~27.1 pg/m3和211.6 pg/m3;6点标准曲线相关系数(r)为0.9980~0.9999。方法对8种目标物的加标回收率为79.1%~101.0%,相对标准偏差(RSD)为4.3%~14.3%(n=6)。对6份南京实际大气样品的检测结果表明:离子阱质谱的选择反应监测(selected reaction monitoring,SRM)技术能有效的降低背景干扰。优化后的MS/MS方法对目标化合物有较高的灵敏度,可应用于大气中痕量多溴二苯醚的定量检测。     

微波辅助萃取-衍生气相色谱-电子捕获检测器法测定电子电气产品中的四溴双酚A

以N,O-双(三甲基硅烷基)三氟乙酰胺(BSTFA)作衍生化试剂,采用微波辅助萃取-衍生气相色谱-电子捕获检测器法(GC-ECD)测定电子电气产品中的四溴双酚A。使用V(甲苯)∶V(甲醇)=10∶1微波辅助萃取电子电气样品,用正己烷沉淀萃取液中的高聚物,净化后,将萃取液进行衍生化反应,采用ECD检测器进行定量测定。对衍生化时间、衍生化温度、衍生化试剂用量、沉淀试剂用量等前处理条件进行了优化,并进行了线性、回收率、精密度等试验。结果表明,方法线性范围为0.005~5 mg/L,相关系数为0.9985,方法的检测下限为0.02 mg/kg。采用样品加标的方式进行四溴双酚A的精密度及回收率实验,回收率在81.7%~110%之间,相对标准偏差RSD(n=7)小于7.2%。所建方法能很好的应用于电子电气产品中四溴双酚A的检测。     

Versatile and fast gas chromatographic determination of frequently used brominated flame retardants in styrenic polymers

Two versatile and fast methods to identify and quantify brominated flame retardants (BrFRs) in styrenic polymers were developed. Gas chromatography/mass spectrometry (GC/MS) as well as gas chromatography with electron-capture detection (GC/ECD), both following ultrasonic-supported dissolution and precipitation (USDP), were applied. The substance range includes poly-brominated biphenyls (PBBs) and diphenyl ethers (PBDEs), as well as other commonly used flame retardants (FRs), including two phosphate-based flame retardants. The methods were verified using congener standards and flame-retardant polymer samples. Good recoveries were found. Overall run time for the analysis, including sample preparation, is less than 60min.