Ziarrusta H, Olivares M, Delgado A, Posada-Ureta O, Zuloaga O, Etxebarria N
Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.O. Box 644, 48080 Bilbao, Spain.
Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.O. Box 644, 48080 Bilbao, Spain.
J Chromatogr A. 2015 Apr 24;1391:18-30. doi: 10.1016/j.chroma.2015.02.072. Epub 2015 Mar 6.
This work describes the optimisation, validation and application of matrix solid-phase dispersion (MSPD) coupled to gas chromatography mass spectrometry, both single quadrupole (GC-MS) and tandem (GC-MS/MS), for the quantification in molluscs of up to 40 different analytes belonging to several families of priority and emerging organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs) and musk fragrances. The MSPD procedure was fully optimised with a special focus on the clean-up strategy. The best recoveries were obtained using glass syringes, 0.30 g of freeze-dried sample, 0.30 g of Florisil as solid support, 4.00 g of activated silica and 25 mL of dichloromethane as elution solvent. Using GC-MS/MS the method afforded good linearities (r(2), between 0.980 and 0.9996), adequate repeatability and reproducibility (RSD<17% and 33%, respectively) and low instrumental limits of detection (between 0.010 and 2.74 ng mL(-1)). The accuracy of the method was evaluated using different approaches, i.e. assessment of spiked fish hatchery samples, laboratory reference material and standard reference material (SRM 2977). Satisfactory apparent recoveries were obtained for all the target analytes after correction with the corresponding labelled surrogate, except for PAHs in the case of SRM 2977, which required the use of the standard addition method. Finally, MSPD was applied to mollusc species collected in Colombia and Nicaragua, where PAHs, PCBs, musks and pesticides were detected at low ng g(-1) levels.
本研究描述了基质固相分散（MSPD）与气相色谱 - 质谱联用技术（单四极杆气相色谱 - 质谱联用仪（GC-MS）和串联气相色谱 - 质谱联用仪（GC-MS/MS））的优化、验证及应用，用于定量分析软体动物中多达40种不同的分析物，这些分析物属于多个优先控制和新兴有机污染物类别，包括多环芳烃（PAHs）、多氯联苯（PCBs）、多溴二苯醚（PBDEs）、有机氯农药（OCPs）、有机磷农药（OPPs）和麝香香料。特别关注净化策略，对MSPD程序进行了全面优化。使用玻璃注射器、0.30 g冷冻干燥样品、0.30 g弗罗里硅土作为固体支持物、4.00 g活性二氧化硅和25 mL二氯甲烷作为洗脱溶剂时，获得了最佳回收率。使用GC-MS/MS时，该方法具有良好的线性（r²在0.980至0.9996之间）、足够的重复性和再现性（相对标准偏差分别<17%和33%）以及较低的仪器检测限（在0.010至2.74 ng mL⁻¹之间）。采用不同方法评估了该方法的准确性，即对加标鱼孵化场样品、实验室参考物质和标准参考物质（SRM 2977）进行评估。除SRM 2977中的PAHs需要使用标准加入法外，所有目标分析物在用相应标记替代物校正后均获得了令人满意的表观回收率。最后，MSPD应用于在哥伦比亚和尼加拉瓜采集的软体动物物种，在这些样品中检测到PAHs、PCBs、麝香和农药的含量处于低ng g⁻¹水平。
