Research Group EnVOC, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent, Belgium.
Anal Bioanal Chem. 2012 Feb;402(4):1697-711. doi: 10.1007/s00216-011-5568-0. Epub 2011 Dec 7.
An innovative analytical method based on high-performance liquid chromatography and atmospheric pressure chemical ionization magnetic sector mass spectrometry was developed and optimized to determine trace concentrations of 11 compounds belonging to the group of the seldom-analyzed oxy-PAHs (phenanthrene-9,10-dione, chrysene-5,6-dione, benzo[a]pyrene-4,5-dione, benzo[a]pyrene-1,6-dione, benzo[a]pyrene-3,6-dione, benzo[a]pyrene-6,12-dione, 4-oxa-benzo[def]chrysene-5-one, pyrene-1-carboxaldehyde, benzo[de]anthracene-7-one, benzo[a]anthracene-7,12-dione, and napthacene-5,12-dione) on airborne particulate matter (PM(10)). The mass spectrometer was operated in multiple ion detection mode, allowing for selective accurate mass detection (mass resolution of 12,000 full width at half maximum) of the oxy-PAHs characteristic ions. Optimization of both the vaporizer (450 °C) and capillary temperature (350 °C) resulted into instrumental detection limits in the range between 7 (benzo[a]pyrene-1,6-dione) and 926 pg (benzo[a]anthracene-7,12-dione). The advanced pressurized liquid extraction (PLE) and the more traditionally used ultrasonic extraction (USE) were compared using ethyl acetate as an extraction solvent. For both techniques, high recoveries from spiked quartz fiber filters (PLE, 82-110%; USE, 67-97%) were obtained. Recoveries obtained from real PM(10) samples were also high (76-107%), and no significant matrix effects (ME) on the ionization process (enhancement or suppression) were found (ME, 89-123%). Method limits of quantification (S/N = 10) were in the range between 2 and 336 pg/m(3). This method was used to analyze real PM samples collected at several urban and rural locations in the Antwerp area. For the first time, concentrations for Belgium are provided. Concentrations of individual oxy-PAHs are in the lower pictograms per cubic meter to 6 ng/m(3) range. High concentration differences between individual compounds are found as exemplified by the 75th percentile of the phenanthrene-9,10-dione and benzo[de]anthracene-7-one concentrations being a factor of 4 to 22 higher compared with the other target oxy-PAHs.
建立并优化了一种基于高效液相色谱和大气压化学电离扇形磁场质谱的创新分析方法，用于测定痕量浓度的 11 种化合物，这些化合物属于少见的含氧多环芳烃（苊烯-9,10-二酮、屈-5,6-二酮、苯并[a]芘-4,5-二酮、苯并[a]芘-1,6-二酮、苯并[a]芘-3,6-二酮、苯并[a]芘-6,12-二酮、4-氧杂-苯并[def]屈-5-酮、苝-1-甲醛、苯并[de]蒽-7-酮、苯并[a]蒽-7,12-二酮和萘并[2,3-d]噻吩-5,12-二酮）在空气颗粒物（PM10）上的含量。质谱仪以多离子检测模式运行，可对含氧多环芳烃的特征离子进行选择性准确质量检测（半峰全宽为 12000）。汽化器（450°C）和毛细管温度（350°C）的优化使得仪器检测限在 7（苯并[a]芘-1,6-二酮）到 926 pg（苯并[a]蒽-7,12-二酮）之间。比较了使用乙酸乙酯作为萃取溶剂的加压液体萃取（PLE）和传统的超声波萃取（USE），两种技术都能从石英纤维滤器上获得高回收率（PLE，82-110%；USE，67-97%）。从实际 PM10 样品中获得的回收率也很高（76-107%），而且在离子化过程中没有发现明显的基质效应（增强或抑制）（ME，89-123%）。方法定量限（S/N=10）在 2 到 336 pg/m3 之间。该方法用于分析在安特卫普地区几个城市和农村地点采集的实际 PM 样品。首次提供了比利时的浓度数据。个别含氧多环芳烃的浓度在每立方米几个皮克到 6 纳克之间。个别化合物之间的浓度差异很大，例如，苊烯-9,10-二酮和苯并[de]蒽-7-酮的第 75 百分位数与其他目标含氧多环芳烃相比，浓度高 4 到 22 倍。
