Perkons Ingus, Lazdina Laura, Zacs Dzintars
Institute of Food Safety, Animal Health and Environment "BIOR", Riga, 1076, Latvia.
University of Latvia, Riga, 1004, Latvia.
Anal Bioanal Chem. 2025 Aug 21. doi: 10.1007/s00216-025-06070-0.
Polychlorinated alkanes (PCAs), the principal constituents of chlorinated-paraffin technical mixtures, are persistent, bioaccumulative pollutants that raise growing toxicological concern. Due to their complexity, PCA analysis in food remains analytically challenging, predominantly relying on high-resolution mass spectrometry applications. This study aimed to develop and validate a more accessible liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for quantifying PCA-C in food commodities. Six reversed-phase columns were evaluated during the study, and phenyl-hexyl and biphenyl stationary phases provided superior separation of critical isobaric PCA homologues. Ammonium acetate (5 mM) was used as a mobile phase additive to promote the formation of acetate adducts, enhancing selectivity in MS/MS settings by minimizing the impact of deprotonated species on product-ion spectra. Validation experiments conducted using fortified samples demonstrated satisfactory recoveries (PCA-C, 88%; PCA-C, 121%; and PCA-C, 103%). Comparative analyses using six interlaboratory test materials and a certified fish matrix reference material confirmed the method's accuracy. All z-scores for PCA-C were ≤|2|, and only 2 results for PCA-C were in the questionable range (|z|= 2-3). In the certified reference material, measured values for PCA-C were within the certified range, while those for PCA-C were near its lower boundary. The developed method was compared to the conventional high-resolution mass spectrometry, showing a strong agreement between the results of both instrumental setups. These results establish this LC-MS/MS protocol as an accessible and reliable alternative to PCA monitoring within food safety and regulatory frameworks.
多氯烷烃（PCAs）是氯化石蜡工业混合物的主要成分，是具有持久性、生物累积性的污染物，引发了越来越多的毒理学关注。由于其复杂性，食品中的PCA分析在分析上仍具有挑战性，主要依赖于高分辨率质谱应用。本研究旨在开发并验证一种更易操作的液相色谱-串联质谱（LC-MS/MS）方法，用于定量食品中的PCA-C。研究过程中评估了六种反相柱，苯基己基和联苯固定相能更好地分离关键的等压PCA同系物。使用乙酸铵（5 mM）作为流动相添加剂，以促进乙酸盐加合物的形成，通过最小化去质子化物种对产物离子光谱的影响来提高MS/MS设置中的选择性。使用加标样品进行的验证实验显示回收率令人满意（PCA-C为88%；PCA-C为121%；PCA-C为103%）。使用六种实验室间测试材料和一种经认证的鱼类基质参考材料进行的对比分析证实了该方法的准确性。PCA-C的所有z分数均≤|2|，PCA-C只有2个结果处于可疑范围（|z| = 2 - 3）。在经认证的参考材料中，PCA-C的测量值在认证范围内，而PCA-C的测量值接近其下限。将所开发的方法与传统的高分辨率质谱进行比较，两种仪器设置的结果显示出很强的一致性。这些结果表明，在食品安全和监管框架内，这种LC-MS/MS方案是PCA监测的一种易于操作且可靠的替代方法。
