Key Laboratory of Nature Resource of the Changbai Mountain and Functional Molecular (Yanbian University), Ministry of Education, Park Road 977, Yanji City, Jilin Province, China.
J Chromatogr A. 2012 Apr 27;1235:132-40. doi: 10.1016/j.chroma.2012.02.047. Epub 2012 Feb 28.
The presence of perfluorocarboxylates (PFCAs) in the environment is of increasing concern due to their possible toxicity to humans and bioaccumulation in organisms. PFCAs are frequently found in river water, sediment and organisms and sometimes even in groundwater. In order to quantitatively determine these PFCAs, a fast derivatization coupled with a liquid chromatography-ultraviolet detector-electrospray ionization-tandem mass spectrometry (LC-UV-ESI-MS/MS) method was developed. The PFCAs were quantitatively converted to their corresponding phenacyl esters using p-bromophenacyl bromide as the derivatization reagent. Under optimized reaction conditions, the conversion yield of the PFCAs ranged from 86 to 92% with low %RSD. The typical derivatization product (p-bromophenacyl bromide perfluorooctanoate) was characterized by (1)H NMR, (13)C NMR, FT-IR and mass spectrometry. UPLC with a BEH C18 column and CAN/H(2)O (8/2, v/v) as a mobile phase were used to separate the derivatives. The analytes were completely eluted within 6 min and multidimensional detection using UV at 260 nm and ESI-MRM in the negative ion mode were carried out. Bromide isotopic characteristic fragment ions appeared in the first Q1 scans, and four daughter ions of the MRMs at m/z M-H-222, M-H-250, M-H-278 and M-H-316 were used for quantification and confirmation. The mass spectral information ensured accurate identification of the analytes even when the sample matrices were complex. The method successfully eliminated the PFCAs background problems originating from polymeric parts in liquid chromatographic systems. The LODs of the method were lower than 5 ng mL(-1), and the relative standard deviation (RSD%) values ranged from 5.2 to 9.8%. The method was successfully applied for the quantification of PFCAs in river water contaminated by industrial wastewater, and this indicated that the method was useful in the determination of PFCAs in environmental samples.
全氟羧酸（PFCAs）由于其对人类可能的毒性和在生物体中的生物累积性，在环境中的存在引起了越来越多的关注。PFCAs 经常在河水、沉积物和生物体中被发现，有时甚至在地下水中也能被发现。为了定量测定这些 PFCAs，开发了一种快速衍生化结合液相色谱-紫外检测器-电喷雾电离-串联质谱（LC-UV-ESI-MS/MS）方法。使用对溴苯甲酰溴作为衍生化试剂，将 PFCAs 定量转化为相应的苯甲酰酯。在优化的反应条件下，PFCAs 的转化率范围为 86%至 92%，相对标准偏差（%RSD）较低。典型的衍生化产物（对溴苯甲酰溴全氟辛烷酸酯）通过（1）H NMR、（13）C NMR、FT-IR 和质谱进行表征。采用 BEH C18 柱和 CAN/H（2）O（8/2，v/v）作为流动相的 UPLC 用于分离衍生物。分析物在 6 分钟内完全洗脱，并在负离子模式下采用 UV 260nm 和 ESI-MRM 进行多维检测。溴化物同位素特征碎片离子出现在第一个 Q1 扫描中，MRM 中的四个子离子 m/z [M-H-222]（-）、[M-H-250]（-）、[M-H-278]（-）和[M-H-316]（-）用于定量和确证。质谱信息确保了即使在复杂的样品基质中，也能准确识别分析物。该方法成功消除了来自液相色谱系统聚合部分的 PFCAs 背景问题。该方法的检出限（LODs）低于 5ng/mL，相对标准偏差（RSD%）值在 5.2%至 9.8%之间。该方法成功应用于工业废水污染的河水中 PFCAs 的定量分析，表明该方法在环境样品中 PFCAs 的测定中是有用的。
