Lipičar Eva, Fras Danijela, Javernik Nino, Prosen Helena
National Laboratory of Health, Environment and Food, Centre for Chemical Analysis of Food, Water and Other Environmental Samples, Prvomajska ulica 1, 2000 Maribor, Slovenia.
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1000 Ljubljana, Slovenia.
Toxics. 2022 Dec 24;11(1):15. doi: 10.3390/toxics11010015.
Flame retardants are added to consumer products to retard the ignition of combustible materials. Technical mixtures of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) were massively used for several decades. They are bioaccumulative, persistent, and have adverse effects on organisms. Recognised as persistent organic pollutants, they are banned almost worldwide. Food is the principal source of human exposure. Yet, no maximum residue limits for food have been established in the EU. Nevertheless, monitoring of specific congeners is recommended. Simultaneous analysis of HBCDDs and PBDEs is rarely encountered, especially including BDE-209, as this thermally unstable congener is particularly challenging for analysis. We have developed a method for the simultaneous determination of all relevant PBDEs and HBCDDs recommended for monitoring by the EU. In the method, single sample preparation is used for different types of foodstuffs, applying ultrasound-assisted extraction, clean-up by gel permeation, and adsorption chromatography. Analyses were performed on the same extract, first by GC-MS/MS(EI) method for PBDEs and followed by LC-MS/MS(ESI) method for HBCDDs. The analytical method was validated on a blank sample of milk formula at 2-3 fortification levels, including recommended LOQ level of 0.01 µg/kg wet weight. Satisfactory accuracy with recoveries 85-119%, intra-day precision (1.5-11.3%), and inter-day precision (4.3-18.4%) was obtained. The method ensures LOQs that are compliant with the EU recommendations for all PBDEs and HBCDDs, including BDE-209. Method applicability was further confirmed on proficiency testing samples of baby food, fish, and citrus.
阻燃剂被添加到消费品中以延缓可燃材料的着火。多溴二苯醚（PBDEs）和六溴环十二烷（HBCDD）的技术混合物被大量使用了几十年。它们具有生物累积性、持久性，并对生物体有不利影响。作为持久性有机污染物，它们在全球几乎都被禁止。食物是人类接触这些污染物的主要来源。然而，欧盟尚未制定食品中的最大残留限量。尽管如此，仍建议对特定同系物进行监测。同时分析HBCDDs和PBDEs的情况很少见，特别是包括BDE - 209，因为这种热不稳定的同系物在分析上极具挑战性。我们开发了一种同时测定欧盟建议监测的所有相关PBDEs和HBCDDs的方法。在该方法中，针对不同类型的食品采用单一的样品制备方法，应用超声辅助萃取、凝胶渗透净化和吸附色谱法。对同一提取物进行分析，首先采用GC - MS/MS（EI）法测定PBDEs，然后采用LC - MS/MS（ESI）法测定HBCDDs。该分析方法在2 - 3个强化水平的婴儿配方奶粉空白样品上进行了验证，包括建议的定量限水平0.01 μg/kg湿重。获得了令人满意的准确度，回收率为85 - 119%，日内精密度为（1.5 - 11.3%），日间精密度为（4.3 - 18.4%）。该方法确保了所有PBDEs和HBCDDs（包括BDE - 209）的定量限符合欧盟建议。该方法的适用性在婴儿食品、鱼类和柑橘类的能力验证样品上得到了进一步证实。
