Analysis of polybrominated diphenyl ethers (PBDEs) by liquid chromatography with negative-ion atmospheric pressure photoionization tandem mass spectrometry (LC/NI-APPI/MS/MS): application to house dust

Eight polybrominated diphenyl ether (PBDE) congeners of primary interest to the US EPA were separated using reverse-phase liquid chromatography on an octadecylsilane column. BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209 were baseline-resolved under isocratic conditions in 92:8 methanol/water (v/v). Negative-ion atmospheric pressure photoionization (NI-APPI) with a toluene dopant produced precursor ions corresponding to [M–Br+O]^– for the eight congeners studied. Each congener was quantified by tandem mass spectrometry through a unique multiple reaction monitoring (MRM) transition. On-column limits of detection were between 2.4 and 27.8 pg for the eight congeners studied, with an intra-day method precision of 9%. The LC/NI-APPI/MS/MS method was validated for the analysis of the eight PBDE congeners in NIST SRM 2585 (Organics in House Dust). Pressurized liquid extraction (PLE) with subsequent LC/NI-APPI/MS/MS analysis afforded quantitative recovery for all eight PBDE congeners with recoveries ranging from 92.7 to 113%. The liquid-phase separation of the LC/NI-APPI/MS/MS method is not prone to the thermal degradation issues that plague splitless GC based analyses of highly brominated PBDEs such as BDE-209.     

New perspective on the determination of flame retardants in sewage sludge by using ultrahigh pressure liquid chromatography–tandem mass spectrometry with different ion sources

Analysis of 11 polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A bis 2,3-dibromopropylether (TBBPA-bis), tetrachlorobisphenol A (TCBPA), tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) was optimized by ultrahigh pressure liquid chromatography/tandem mass spectrometry (UPLC–MS/MS) operating in negative ion (NI) mode. Electrospray ionization (ESI), atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) sources were tested and for PBDEs APCI gave higher sensitivity than APPI while for TBBPA-bis APCI and APPI showed similar performance. ESI was the best option for TCBPA, TBBPA and HBCDs. Detection limits were between 20 and 59 fg for the compounds analyzed by ESI, 0.10 and 0.72 pg for PBDEs and 6 pg for TBBPA-bis. The matrix effect of sewage sludge extract was also tested showing negligible ion suppression for APCI and an increase of the background level of all investigated pollutants leading to a worsening of the limits of quantification by a factor between 1.2 and 3.3. The UPLC-APCI/MS/MS method for PBDEs, after pressurized liquid extraction (PLE), was validated by comparison with the concentration values from the NIST 1944 standard reference material. The advantages of the methods include low detection limits, PBDE congeners specificity using selected multiple reaction monitoring (MRM) transitions, and the absence of thermal degradation of higher PBDE congeners, especially BDE-209. The methods were applied for the determination of the above reported flame retardants in sewage sludge in order to get more information about the degradation on PBDEs (in particular BDE-209) during municipal wastewater treatments.     

Determination of polybrominated diphenyl ethers in human hair by gas chromatography-mass spectrometry

A rapid analytical method has been developed for the determination of polybrominated diphenyl ethers (PBDEs) in human hair. PBDEs were determined by gas chromatography with electron ionization mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). A 200 mg amount of hair samples was overnight digested in 3N HCl and then PBDEs extracted with n-hexane. After clean up of extracts in a Florisil column, PBDEs were analyzed by GC-MS. The method has been validated by spiking human hair at five concentration levels, in the range from 5 to 25 ng/g for most compounds, and PBDEs were quantified using labelled compounds as internal standards. Recoveries of PBDEs were higher than 90%, repeatability was equal or lower than 12.5%, and reproducibility lower than 14%, expressed as relative standard deviation (RSD). Limits of detection (LOD) were in the range 0.08-0.9 ng/g and limits of quantification (LOQ) were between 0.27 and 3.0 ng/g. This method was applied to the determination of PBDEs in hair samples from 16 individuals and 5 PBDE congeners were detected in most of the samples. BDE-209 was the dominant compound found, followed by BDE-47, BDE-99, BDE-100, and BDE-190. BDE-209 was found in 12 out of 16 hair samples, and the total levels of PBDEs ranged from 1.4 to 19.9 ng/g.     

Determination of 41 polybrominated diphenyl ethers in soil using a pressurised solvent extraction and GC-NCI-MS method

A rapid and reliable analytical method based on pressurised solvent extraction (PSE) and GC-NCI-MS was developed for the determination of 41 different PBDEs in soil. All PBDEs, including mono- to hepta-BDEs (sum of 39 congeners), one nona-BDE and deca-BDE, were efficiently extracted from soil samples using the extraction technology of PSE. The extract was then cleaned up on a florisil column. Satisfactory separation of 41 PBDE congeners was obtained on a 15-m DB-5MS capillary column, saving the use of another 30-m column specific for the separation of mono- to hepta-BDEs. PBDEs were identified and quantified by GC-MS in negative chemical ionisation (NCI) mode, and further confirmed in semi electron impact (SEI) mode when the ion source was also NCI. The method detection limits ranged from 0.01 to 0.03?ng?g^?1?dw for mono- to hepta-BDEs, 1.43?ng?g^?1?dw for the nona-BDE and 0.20?ng?g^?1?dw for deca-BDE. The applicability of the method was tested in soil samples collected from an e-waste recycling site at Guiyu. Twenty-one PBDEs (mono- to deca-) were detected, and eighteen congeners were quantified. The concentration range of PBDEs was 0.78–436?ng?g^?1?dw. BDE-47, BDE-99, BDE-153, BDE-183, BDE-206 and BDE-209 were the dominant congeners, and BDE-209 accounted for 62% of the total PBDEs. The congener profiles of PBDEs in soil samples were similar to those in three commercial PBDE products (Penta-, Octa- and Deca-BDE), and Deca-BDE product was the most important contributor.     

Fast analysis of decabrominated diphenyl ether using low-pressure gas chromatography-electron-capture negative ionization mass spectrometry

This paper reports the applicability of low-pressure gas chromatography-mass spectrometry operated in electron-capture negative ionization mode (LP-GC-ECNI-MS) for the analysis of decabrominated diphenyl ether (BDE-209). Particular attention was paid to find optimal injector and oven conditions for minimal thermal degradation of BDE-209. The analytical characteristics were compared for LP-GC columns (10 m x 0.53 mm) with different film thicknesses (d(f) 0.15 microm versus 0.25microm) and for a conventional GC column (15 m x 0.25 mm, 0.10 microm d(f)). Short residence times (6.5 and 9.8 min) of BDE-209 were found for the LP-GC systems with 0.15 and 0.25microm d(f), respectively, resulting in a low elution temperature and minimal degradation. Additionally, baseline separation of 22 polybrominated diphenyl ether (PBDE) congeners (major components of PBDE technical mixtures) was possible in less than 12 min using the LP-GC-ECNI-MS system with 0.15microm d(f). The optimized method was applied for the determination of PBDEs in Belgian indoor dust samples. The obtained concentrations of BDE-209 (range 8-292 ng/g dry weight) were in the same range or lower than concentrations in dust from other European countries.     

Factorial-design optimization of gas chromatographic analysis of tetrabrominated to decabrominated diphenyl ethers. Application to domestic dust

Gas chromatographic analysis of polybrominated diphenyl ethers (PBDEs) has been evaluated in an attempt to achieve better control of the separation process, especially for highly substituted congeners. Use of a narrow-bore capillary column enabled adequate determination of tetra, penta, hexa, hepta, octa, nona and decaBDE congeners in only one chromatographic run while maintaining resolution power similar to that of conventional columns. A micro electron-capture detector (GC–μECD) was used. Chromatographic conditions were optimized by multifactorial experimental design, with the objective of obtaining not only high sensitivity but also good precision. In this way two different approaches to maximizing response and minimizing variability were tested, and are fully discussed. These optimum chromatographic conditions were then used to determine PBDEs extracted from domestic dust samples by microwave-assisted solvent extraction (MASE). Quantitative recovery (90–108%) was achieved for all the PBDEs and method precision (RSD < 13%) was satisfactory. Accuracy was tested by use of the standard reference material SRM 2585, and sub-ng g⁻¹ limits of detection were obtained for all compounds except BDE-209 (1.44 ng g⁻¹). Finally, several samples of house dust were analysed by use of the proposed method and all the target PBDEs were detected in all the samples. BDE-209 was the predominant congener. Amounts varied from 58 to 1615 ng g⁻¹ and the average contribution to the total PBDE burden of 52%. The main congeners of the octaBDE mixture (BDE-183, BDE-197, BDE-207 and BDE-196) also made an important contribution (29%) to the total. These are the first data about the presence of these compounds in European house-dust samples. Finally, the sum of the main congeners in the pentaBDE commercial mixture (BDE-47, BDE-99, and BDE-100) contributed 14% to the total. Figure Polybrominated diphenyl ethers in House Dust     

超声辅助萃取-气相色谱-负化学电离源质谱法测定室内灰尘样品中8种常见多溴联苯醚

建立了室内灰尘样品中8种常见多溴联苯醚(PBDEs: BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)的气相色谱-负化学电离源质谱(GC-NCI/MS)分析方法。样品经吸尘器采集、正己烷超声萃取、浓缩后,采用GC-NCI/MS测定。结果表明,方法的加标回收率为53.2%～107.6%,日内测定的相对标准偏差(RSD)为2.8%～16.5%,日间测定的RSD为6.4%～22.6%。除了BDE-209的检出限(信噪比为3)为0.15 ng/g外,其他多溴联苯醚的检出限为0.003～0.015 ng/g。该方法灵敏度高,准确度和精密度好,简便快速,溶剂消耗量少,适用于灰尘中三溴～十溴联苯醚的测定。     

Microwave-assisted extraction (MAE) for the determination of polybrominated diphenylethers (PBDEs) in sewage sludge

An efficient microwave-assisted extraction (MAE) method has been developed and evaluated for the quantification of eight major polybrominated diphenylethers (PBDEs) in sewage sludge. The PBDEs were extracted from wet and dry sludge in a microwave extraction unit using a hexane/acetone mixture for 35 min at a controlled temperature of 130 °C. The extract was concentrated, cleaned up on a silica gel column, and analyzed by gas chromatography/mass spectrometry (GC/MS) in the negative chemical ionization (NCI) mode. The MAE procedure exhibited higher extraction efficiency, specifically for BDE (brominated diphenylether) 209, than the conventional Soxhlet extraction. The test congeners were clearly separated under specific instrumental operating conditions, at a source temperature of 230 °C and a column length of 20 m. The present analytical method showed recovery efficiencies ranging from 80 to 110% when applied to the PBDE-free sludge spiked with eight PBDE congeners. The efficiency of the MAE method was confirmed using sludge obtained from four sewage treatment plants (STPs). The results indicate that BDE 47, 99, and 209 are the most abundant congeners present in these sewage sludges, which is consistent with previous reports.     

超声辅助萃取气相色谱-质谱法测定松针中的多溴联苯醚

建立了测定松针样品中多溴联苯醚(PBDEs)的分析方法。松针样品经过正己烷-丙酮(体积比为1∶1)混合溶液超声萃取、浓硫酸和氧化铝柱净化后,采用气相色谱-负化学电离源质谱(GC-NCI-MS)选择离子监测(SIM)模式检测,内标法定量。结果表明,方法的加标回收率为83.8%~107.5%,三溴~七溴代联苯醚的仪器检出限为0.152~ 0.770 pg,十溴代联苯醚(BDE-209)的检出限为11.1 pg;三溴~七溴代联苯醚的方法检出限(湿重)为3~15 pg/g,BDE-209的方法检出限(湿重)为222 pg/g。方法具有良好的重现性、较高的灵敏度和良好的回收率。实际样品分析表明,松针中BDE-209是主要的同类物,约占8种PBDEs总量的82.3%,低溴代联苯醚以2,2′,4,4′-四溴联苯醚(BDE-47)为主。     

Determination of Polybrominated Diphenyl Ethers in Coastal and River Sediments by Pressurized Liquid Extraction Coupled with Gas Chromatography‐Mass Spectrometry

This study presents a time‐ and solvent‐saving method, pressurized liquid extraction (PLE), to extract polybrominated diphenyl ethers (PBDEs) in sediment samples. The effects of various operating parameters (i.e., extraction solution, temperature, pressure, static/dynamic extraction times) for the quantitative extraction of PBDEs by home‐made PLE were systematically investigated and optimized. The analytes were then identified and quantitated by gas chromatography‐mass spectrometry (GC‐MS) in selected ion monitoring (SIM) mode. The 16 PBDE congeners (from tri‐ to deca‐BDE) can be completely extracted by dichloromethane: n‐hexane (3/2, v/v) at 100 °C and 100 atm combined with 15 min static and then 15 min dynamic extraction steps. Recovery of PBDEs in spiked sediment samples ranged from 52 to 104% with 2‐16% RSD, except for BDE‐206. Limits of quantitation (LOQ) were established between 4 and 400 pg/g (dry weight) in 10 g of sediment sample. The extraction efficiency of the PLE was also compared with the traditional Soxhlet extraction method. The total contents of PBDEs ranged from 8.0 to 37.9 ng/g (dry weight) in various river and coastal sediment samples in Taiwan. Deca‐BDE (BDE‐209) was the major PBDE detected in these sediment samples.     

鱼肉组织中多溴联苯醚的定量分析

多溴联苯醚(PBDEs)是一类广泛用于家用电器、电子产品、塑料泡沫、家居装饰材料等行业的添加型阻燃剂[1],使用量最多的是五溴联苯醚(penta-BDE),八溴联苯醚(octa-BDE)和十溴联苯醚(deca-BDE)3种[2]。最近的研究表明[4-6],多溴联苯醚已广泛地存在于各种环境介质、生物体及人体中     

An organically modified silicate molecularly imprinted solid-phase microextraction device for the determination of polybrominated diphenyl ethers

An organically modified silicate (ORMOSIL) SPME stationary phase molecularly imprinted with BDE-209 has been successfully fabricated by conventional sol-gel technique from phenyltrimethoxysilane and tetraethoxysilane. The thickness of the ORMOSIL-SPME stationary phase, on fused-silica optical fibres, was measured to be ca. 9.5 μm with a volume of ca. 0.12 μL. Rebinding assays and Scatchard analysis revealed that the imprinted ORMOSIL-SPME stationary phase possessed a binding affinity, K_B, of 7.3 ± 1.7 × 10¹⁰ M⁻¹ for BDE-209, with a receptor site density, B_max, of 1.2 × 10⁻³ pmol per SPME device. Besides its molecular template, the ORMOSIL-SPME stationary phase also showed good affinity (log K_B ≥ 9.5) for smaller BDE congeners commonly found in the natural environment. The density of receptor sites within the imprinted matrix for those smaller BDE congeners was even higher than that for BDE-209. This may be attributable to the binding site heterogeneity of the imprinting process that creates deformed binding sites that are suitable for the accommodation of the smaller BDE congeners. Compared to the commercially available polyacrylate and polydimethylsiloxane SPME stationary phases, the imprinted ORMOSIL-SPME devices showed much higher pre-concentration ability towards polybrominated diphenyl ethers (PBDEs), even in direct immersion sampling at room temperature. Coupled with GC-NCI-MS and GC-μECD, the imprinted ORMOSIL-SPME device was able to achieve detection sensitivity of 0.2-3.6 pg mL⁻¹ and 1-8.8 pg mL⁻¹, respectively, for commonly occurring BDE congeners, including medium to high molecular weight PBDEs. The imprinted ORMOSIL-SPME device has been successfully applied to monitor PBDE contents in municipal wastewaters.     

Feasibility of electron impact and electron capture negative ionisation mass spectrometry for the trace determination of tri- to deca-brominated diphenyl ethers in human samples

The applicability of two different MS ionisation modes (EI and ECNI) for the determination of PBDEs at low-trace levels in small-size (up to 1 mL) human samples was compared. The instrumental precision, expressed as R.S.D., obtained for both ionisation modes was similar and lower than 6% (repeatability) and 12% (intermediate precision) for all congeners investigated, except PBDE 209. The LODs obtained when using the ECNI-MS operation mode (6-507 fg) were lower than those found in EI-MS experiments (9 and 10,909 fg), mainly for those congeners with a high bromination degree, i.e., hepta- to deca-BDEs. The selectivity of the ECNI-MS method proposed in the present work was improved by using two ions of the [M−H_xBr_y]⁻ cluster as both qualifier and quantifier ions. For the final validation of the methods, serum and breast milk samples from two different inter-laboratory exercises were analysed. A good agreement was found between the results obtained using the proposed methods and the results provided by the different inter-laboratory organisations, but only ECNI-MS provided the low-LODs necessary for the quantification of high brominated congeners (mainly, PBDEs 196, 197 and 209) at low concentration levels in small-size human samples. Finally, the ECNI-MS method was applied to real-life samples obtained from the Spanish population and the preliminary results obtained were in the same range as those found in other European and Asian regions and lower than the concentrations reported in USA populations.     

Polybrominated diphenyl ethers (PBDEs) in marine sediment of Thermaikos Gulf,Greece

Polybrominated diphenyl ether (PBDE) concentrations were determined in marine sediment samples collected from 7 different locations around Thermaikos Gulf in north Greece. PBDEs were detected in all sampling sites and their average total concentration (ΣPBDEs) ranged from 0.26 to 4.92?ng?g^?1?d.w. Concentrations were an order of magnitude higher in locations outlining the inner part of the Gulf, which were also closer to industrial areas, sewage treatment plant discharges, the city's harbour and landfill area. These findings suggest pollution in the aquatic ecosystem from industrial and urban activities in the area. Congener profiles exhibit predominance of BDE-209, while concentrations of other PBDE congeners were usually lower, when compared to similar studies from other countries globally, indicating that Thermaikos Gulf is among the low-polluted areas. Statistical analysis showed significant differences among the higher polluted sampling stations. Statistically significant differences also existed between sampling stations with high and low PBDE concentrations. Correlations between congeners suggested local contamination sources; however, specific point sources of pollution were not established.     

Dispersive liquid-liquid microextraction followed by reversed phase-high performance liquid chromatography for the determination of polybrominated diphenyl ethers at trace levels in landfill leachate and environmental water samples

A simple, rapid and efficient method, dispersive liquid-liquid microextraction (DLLME), has been developed for the extraction and preconcentration of polybrominated diphenyl ethers (PBDEs) in water samples. The factors influencing microextraction efficiencies, such as the kind and volume of extraction and dispersive solvent, the extraction time and the salt effect, were optimized. Under the optimum conditions (sample volume: 5 mL; extraction solvent: tetrachloroethane, 20.0 μL; dispersive solvent: acetonitrile, 1.00 mL; extraction time: below 5 s and without salt addition), the enrichment factors and extraction recoveries were high and ranged from 268 to 305 and 87.0 to 119.1%, respectively. Linearity was observed in the range 0.05-50 ng mL⁻¹ for BDE-28 and BDE-99, and 0.1-100 ng mL⁻¹ for BDE-47 and BDE-209, respectively. Coefficients of correlation (r²) ranged from 0.9995 to 0.9999. The repeatability study was carried out by extracting the spiked water samples at concentration levels of 50 ng mL⁻¹ for BDE-28 and BDE-99, and 100 ng mL⁻¹ for BDE-47 and BDE-209, respectively. The relative standard deviations (R.S.D.s) varied between 3.8 and 6.3% (n = 5). The limits of detection (LODs), based on signal-to-noise ratio (S/N) of 3, ranged from 12.4 to 55.6 pg mL⁻¹ (the wavelength of detector at 226 nm). The relative recoveries of PBDEs from tap, lake water and landfill leachate samples at spiking levels of 5, 10 and 50 ng mL⁻¹ were in the range of 89.7-107.6%, 114.3-119.1% and 87.0-90.9%, respectively. As a result, this method can be successfully applied for the determination of PBDEs in landfill leachate and environmental water samples.     

Determination of polybrominated diphenyl ethers in indoor dust standard reference materials

Polybrominated diphenyl ethers (PBDEs) have been measured for the first time in three different indoor dust Standard Reference Materials (SRMs) prepared by the National Institute of Standards and Technology (NIST). Two of these, SRM 2583 (Trace Elements in Indoor Dust) and SRM 2584 (Trace Elements in Indoor Dust), have been certified previously for lead and other inorganic constituents. A third, SRM 2585 (Organics in Indoor Dust), is a new indoor dust reference material prepared by NIST which will be certified for various organic compounds (polycyclic aromatic hydrocarbons, pesticides and polychlorinated biphenyls) in 2005 including certified concentrations for 16 individual PBDE congeners and reference values for an additional three PBDE congeners. Dust SRMs were analyzed for 30 PBDE congeners using high-resolution gas chromatography combined with low-resolution mass spectrometry operated in both negative chemical ionization (GC/ECNI–MS) and electron impact ionization (GC/EI–MS) modes. Sensitivity was an order of magnitude higher using GC/ECNI–MS relative to GC/EI–MS. These SRMs have been characterized and compared to the three PBDE commercial products (pentaBDE, octaBDE and decaBDE). PentaBDE and DecaBDE were present in all three SRMs and were the dominant commercial products, making up approximately 33% and 58%, respectively. Recent studies suggest that house dust may be a leading source of human exposure to PBDEs. These SRMs are the first reference materials with certified concentrations for PBDEs, which will aid in validating future measurements of PBDEs in house dust and other similar matrices. Electronic Supplementary Material Supplementary material is available for this article at http://dx.doi.org/ 10.1007/s00216-005-0227-y     

超声辅助碱解萃取-气相色谱-电子捕获检测器测定海洋沉积物中8种多溴联苯醚

将超声辅助碱液分解杂质与溶剂萃取相结合,采用气相色谱-电子捕获检测(GC-ECD)建立了一种快速高效净化、萃取海洋沉积物中8种常见多溴联苯醚(PBDEs)的分析方法。样品在2.00 mol/L NaOH甲醇溶液中超声30 min,经正己烷萃取、单层硅胶净化、正己烷洗脱、旋蒸浓缩后定容至100 μL,采用GC-ECD分析。结果表明,PBDEs各单体的加标回收率为63.6%~110.3%,相对标准偏差(RSD)为1.7%~15.5%(n=5);十溴联苯醚(BDE-209)的检出限为0.097 ng/g,其他7种单体的检出限为0.002~0.011 ng/g(信噪比为3)。该方法的准确度和精密度较高,稳定性和回收率良好,可满足沉积物中PBDEs的分析要求。利用建立的方法测定了渤海表层沉积物中PBDEs的含量,8种PBDEs总含量在1.566~6.760 ng/g之间,其中BDE-209的含量为1.461~6.438 ng/g,总体呈现出由近岸向远岸递减的趋势,表明人为活动、表层冲刷和陆地河流的输入对渤海地区PBDEs的含量有重要影响。     

Determination of polybrominated diphenyl ethers in freshwater fishes from a river polluted by e-wastes

Analytical method using mass spectrometric techniques was applied for the determination of polybrominated diphenyl ethers (PBDEs) in freshwater fishes. Fish samples collected from Nanyang River contaminated by the recycling electron-wastes (e-wastes) materials were prepared by using Soxhlet extraction and multiple-step column chromatographic clean-up. PBDEs were determined by gas chromatography (GC) coupled with ion trap mass spectrometry (for mono- to hepta-BDEs) and quadrupole mass spectrometry (for BDE-209). The method performance was evaluated with the recovery of ¹³C-labeled internal standards and with the analysis of certified reference biota. The obtained recoveries ranged from 75 to 125% with a relative standard deviation of lower than 10% for 16 PBDE congeners. The total PBDE (ΣPBDE) concentrations in fishes showed the following trend: grass carp < mud carp < crucian carp < silver carp < carp. ΣPBDE concentrations in the abdomen, back and tail muscles of carp ranged from 766, 458 and 530 ng/g w.w., and 53, 52, 45 ng/g w.w. in grass carp, respectively. The ΣPBDE concentrations in abdomen muscles were no significantly higher than in back and tail muscles in carp, crucian carp, grass carp and mud carp. PBDE congener concentrations in muscles correlated well with their lipid content. BDE-47 and BDE-28 were the most abundant congeners followed by BDE-17, BDE-15, BDE-66, BDE-154 and BDE-153 in fishes collected from Guiyu.     

固相萃取-气相色谱-负化学源质谱法测定人血清中的多溴联苯醚

采用OasisHLB固相萃取柱萃取血清中的多溴联苯醚(PBDEs),经浓硫酸柱上除脂后,利用气相色谱-负化学源质谱法测定BDE-17、28、47、66、99、100、153、154、183和209共10种PBDEs组分。BDE-209的测定采用DB-5 ms色谱柱(15 m×0.25 mm×0.1 μm),其他组分采用VF-5 ms色谱柱(30 m×0.25 mm×0.25 μm)。对样品中蛋白质的去除溶剂和固相萃取条件(如洗脱溶剂及其用量)进行了优化。胎牛血清中的加标回收试验结果显示,各PBDEs单体相对于内标的平均回收率为78.5%～109.7%,日内测定的相对标准偏差(RSD)为0.3%～7.4%,日间测定的RSD为1.4%～14.1%。胎牛血清中三溴～七溴联苯醚的检出限(信噪比为3)为0.10～0.27 ng/L;定量限(信噪比为10)除了BDE-209为7.91 ng/L外,其他PBDEs为0.35～0.91 ng/L。采用本方法测定标准参考物质SRM1957和SRM1958,结果在参考值范围内。实验结果表明,本方法灵敏度高、准确度和精密度好,简便快速,溶剂消耗量少,适用于人体血清中三至十位溴取代联苯醚的测定。     

Determination of polybrominated diphenyl ethers in fish tissues by matrix solid-phase dispersion and gas chromatography coupled to triple quadrupole mass spectrometry: Case study on European eel (Anguilla anguilla) from Mediterranean coastal lagoons

This paper describes the development and validation of an analytical methodology to determine 28 polybrominated diphenyl ethers (PBDEs) in European eel (Anguilla anguilla) tissues using matrix solid-phase dispersion (MSPD) and gas chromatography coupled to triple quadrupole mass spectrometry (GC-QQQ-MS/MS). A total of 28 PBDEs were targeted, including tri- to deca-brominated congeners.The robustness and effectiveness of the proposed sample preparation procedure was demonstrated in lipid-rich eel tissues. The use of batch MSPD with activated silica gel and H₂SO₄-impregnated silica gel, followed by H₂SO₄ digestion and multilayer cartridge clean-up allowed for complete lipid removal and eliminated matrix effects during GC-QQQ-MS/MS analysis. The average PBDE recoveries from eel muscle samples spiked with PBDEs at two levels were in the range 56.2-119.0%. Precision was satisfactory since relative standard deviations were lower than 19.6%, regardless of spike level, and method quantification limits ranged between 1 and 170 pg g⁻¹ (wet weight).The method demonstrated its successful application for the analysis of eel samples from two coastal lagoons located on the western French Mediterranean coast. All samples tested positive, but for tri- to hexa-brominated congeners only and total PBDE levels observed in this study were in the range 0.08-1.80 ng g⁻¹ wet weight.