Environmental and Molecular Toxicology Department, Agricultural and Life Sciences Building, Oregon State University, Rm 1007, Corvallis, OR, 97331, USA.
Anal Bioanal Chem. 2013 Nov;405(27):8885-96. doi: 10.1007/s00216-013-7319-x. Epub 2013 Sep 5.
We developed two independent approaches for separation and quantitation of 24 oxygenated polycyclic aromatic hydrocarbons (OPAHs) using both liquid chromatography-atmospheric pressure chemical ionization/mass spectrometry (LC-APCI/MS) and gas chromatography-electron impact/mass spectrometry (GC-EI/MS). Building on previous OPAH research, we examined laboratory stability of OPAHs, improved existing method parameters, and compared quantification strategies using standard addition and an internal standard on an environmental sample. Of 24 OPAHs targeted in this research, 19 compounds are shared between methods, with 3 uniquely quantitated by GC-EI/MS and 2 by LC-APCI/MS. Using calibration standards, all GC-EI/MS OPAHs were within 15 % of the true value and had less than 15 % relative standard deviations (RSDs) for interday variability. Similarly, all LC-APCI/MS OPAHs were within 20 % of the true value and had less than 15 % RSDs for interday variability. Instrument limits of detection ranged from 0.18 to 36 ng mL(-1) on the GC-EI/MS and 2.6 to 26 ng mL(-1) on the LC-APCI/MS. Four standard reference materials were analyzed with each method, and we report some compounds not previously published in these materials, such as perinaphthenone and xanthone. Finally, an environmental passive sampling extract from Portland Harbor Superfund, OR was analyzed by each method using both internal standard and standard addition to compensate for potential matrix effects. Internal standard quantitation resulted in increased precision with similar accuracy to standard addition for most OPAHs using 2-fluoro-fluorenone-(13)C as an internal standard. Overall, this work improves upon OPAH analytical methods and provides some considerations and strategies for OPAHs as focus continues to expand on this emerging chemical class.
我们开发了两种独立的方法，分别使用液相色谱-大气压化学电离/质谱（LC-APCI/MS）和气相色谱-电子轰击/质谱（GC-EI/MS），用于分离和定量 24 种含氧多环芳烃（OPAHs）。基于之前的 OPAH 研究，我们考察了 OPAHs 的实验室稳定性，改进了现有的方法参数，并比较了使用标准添加和环境样品内标物的定量策略。在本研究中，我们共针对 24 种 OPAHs，其中 19 种化合物在两种方法中都能定量，3 种化合物只能用 GC-EI/MS 定量，2 种化合物只能用 LC-APCI/MS 定量。用校准标准品进行定量，所有 GC-EI/MS 定量的 OPAHs 与真实值的偏差都在 15%以内，日内变异性的相对标准偏差（RSD）小于 15%。类似地，所有 LC-APCI/MS 定量的 OPAHs 与真实值的偏差都在 20%以内，日内变异性的 RSD 小于 15%。仪器检测限（LOD）在 GC-EI/MS 上为 0.18 至 36ng/mL，在 LC-APCI/MS 上为 2.6 至 26ng/mL。两种方法都对 4 种标准参考物质进行了分析，并报告了一些以前在这些物质中没有发表过的化合物，如苊酮和呫吨酮。最后，我们分别用两种方法对来自俄勒冈州波特兰港超级基金的环境被动采样提取物进行了分析，使用内标物和标准添加物来补偿潜在的基质效应。对于大多数 OPAHs，使用 2-氟芴酮-（13）C 作为内标物进行内标物定量，可以提高精度和准确度。总的来说，本工作改进了 OPAH 的分析方法，并提供了一些关于 OPAHs 的考虑因素和策略，因为对这一新兴化学类别的关注还在继续扩大。
