Istituto Zooprofilattico Sperimentale dell'Umbria e delle Marche, Via Cupa di Posatora 3, 60131, Ancona, Italy.
Anal Bioanal Chem. 2020 Jan;412(2):397-411. doi: 10.1007/s00216-019-02250-x. Epub 2019 Dec 3.
An analytical method for the simultaneous determination of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in fish, shellfish and muscle of terrestrial animals was developed as an extension of a previously validated method for PBDE analysis. A single sample preparation based on QuEChERS-like extraction and a two-step clean-up, followed by a dual instrumental detection, was implemented. GC-MS/MS was used for PBDEs and LC-MS/MS for HBCDs. The method allows the quantification of fifteen PBDEs (28, 47, 49, 66, 77, 85, 99, 100, 138, 153, 154, 183, 197, 206, 209) and three HBCD isomers (α, β and γ), reaching 10 pg/g LOQs for all the analytes except BDE 206 and 209 (100 pg/g LOQ). The validated method was applied to the analysis of 12 fish and shellfish species (sole, spiny dogfish, smooth-hound, mackerel, swordfish, grey mullet, cod, anchovy, red mullet, Atlantic horse mackerel, tuna fish and mussel) collected in central Italian markets accounting for a total of 44 samples. Generally, ΣPBDEs showed higher concentration than ΣHBCDs except in the case of mussels in which ΣHBCDs > ΣPBDEs. Cod and smooth-hound are the least contaminated species among those analysed in the present study, whereas the highest brominated flame retardant (BFR) levels were found in spiny dogfish samples. The measured contamination levels were generally comparable to or lower than those already published in European studies. Literature data for HBCDs in European fish and shellfish were hard to find; therefore, PBDE and HBCD levels were also compared with European Environmental Quality Standard (EQS) in biota (Directive 2013/39/EU). EQSs for HBCDs are six orders of magnitude higher than those for PBDEs; therefore, while no exceedance was observed for the first, almost all the samples analysed for PBDEs were above EQSs. The presented preliminary data on PBDEs and HBCDs are among the first published in marine fish and shellfish commercialised in Central Italy. Graphical abstrac.
建立了一种同时测定鱼类、贝类和陆生动物肌肉中多溴二苯醚（PBDEs）和六溴环十二烷（HBCDs）的分析方法，作为先前验证的 PBDE 分析方法的扩展。采用基于 QuEChERS 类似提取的单一样品制备和两步净化，随后进行双仪器检测。GC-MS/MS 用于 PBDEs，LC-MS/MS 用于 HBCDs。该方法可定量测定 15 种 PBDEs（28、47、49、66、77、85、99、100、138、153、154、183、197、206、209）和 3 种 HBCD 异构体（α、β 和 γ），除 BDE 206 和 209（100 pg/g LOQ）外，所有分析物的 LOQ 均达到 10 pg/g。验证后的方法应用于意大利中部市场采集的 12 种鱼类和贝类（比目鱼、尖吻鲛、平滑无须鲛、鲭鱼、箭鱼、蓝圆鲹、鳕鱼、凤尾鱼、红鲷鱼、大西洋马鲛鱼、金枪鱼和贻贝）分析，共 44 个样本。一般来说，ΣPBDEs 的浓度高于 ΣHBCDs，除贻贝外，ΣHBCDs > ΣPBDEs。在本研究分析的物种中，鳕鱼和平滑无须鲛是受污染程度最低的物种，而尖吻鲛样本中发现的溴化阻燃剂（BFR）水平最高。测量的污染水平与欧洲研究中已经公布的水平相当或更低。在欧洲鱼类和贝类中有关 HBCDs 的文献数据很难找到；因此，还将 PBDE 和 HBCD 水平与生物群中的欧洲环境质量标准（EQS）（指令 2013/39/EU）进行了比较。HBCDs 的 EQS 比 PBDEs 高六个数量级；因此，虽然第一个 EQS 没有超标，但几乎所有分析的 PBDEs 样本都超过了 EQS。本研究初步报告的关于 PBDEs 和 HBCDs 的数据是意大利中部商业销售的海洋鱼类和贝类中首批公布的数据之一。
