Department of Chemistry, College of Arts and Sciences, University of Alaska Anchorage, 3211 Providence Dr., Anchorage, AK 99508, USA.
Department of Biological Sciences, College of Arts and Sciences, University of Alaska Anchorage, 3211 Providence Dr., Anchorage, AK 99508, USA.
Chemosphere. 2024 May;356:141794. doi: 10.1016/j.chemosphere.2024.141794. Epub 2024 Apr 3.
With new oil and gas lease sales in high-latitude regions, there exists a need to better understand the chemical fate of spilled oil and its effects on biological life. To address this need, laboratory simulations of crude oil spills under sub-Arctic conditions were conducted using artificial seawater and exposure to solar irradiation to create Hydrocarbon Oxidation Products (HOPs). HOPs characterization and their biological effects were assessed using ultra high-performance liquid chromatography (UHPLC) with high resolution mass Orbitrap spectrometry and the aryl hydrocarbon receptor (AhR) chemically activated luciferase gene expression (CALUX) assay. Non-target UHPLC-Orbitrap mass spectrometry analysis identified 251 HOPs that were in greater abundance in light-exposed samples than dark controls. Oxidized polycyclic aromatic hydrocarbons were also detected, including phenanthrene quinone, anthraquinone, hydroxyanthraquinone, and 9-fluoreneone. The composition of HOPs were consistent with photo-products of alkylated two to four ring PAHs, primarily compounds between 1 and 3 aromatic rings and 1-3 oxygens. The HOP mixture formed during photochemical weathering of Cook Inlet crude oil induced greater AhR activity than parent petroleum products solubilized in dark controls, indicating that HOPs, as a complex mixture, may contribute to petroleum toxicity more than the parent petroleum compounds. These non-targeted approaches provide the most comprehensive analysis of hydrocarbon oxidation products to date, highlighting the diversity of the complex mixture resulting from the photooxidation of crude oil and the limitations of targeted analyses for adequately monitoring HOPs in the environment. Taken together, these data identify a critical "blind spot" in environmental monitoring and spill clean-up strategies as there is a diverse pool of HOPs that may negatively impact human and ecosystem health.
随着在高纬度地区进行新的石油和天然气租赁销售，有必要更好地了解溢油的化学命运及其对生物生命的影响。为了满足这一需求，在亚北极条件下使用人工海水和暴露在太阳辐射下进行了模拟原油泄漏的实验室模拟，以产生碳氢化合物氧化产物（HOP）。使用超高效液相色谱（UHPLC）与高分辨率轨道阱质谱联用和芳烃受体（AhR）化学激活荧光素基因表达（CALUX）测定法对 HOP 的特征及其生物效应进行了评估。非靶向 UHPLC-Orbitrap 质谱分析鉴定出 251 种 HOP，其在光照暴露样品中的丰度高于黑暗对照。还检测到氧化多环芳烃，包括菲醌、蒽醌、羟基蒽醌和 9-芴酮。HOP 的组成与烷基化二到四环 PAHs 的光产物一致，主要是 1 到 3 个芳环和 1-3 个氧的化合物。库克湾原油光化学风化过程中形成的 HOP 混合物比黑暗对照中溶解的母体石油产品诱导更大的 AhR 活性，这表明 HOP 作为一种复杂混合物，可能比母体石油化合物对石油毒性的贡献更大。这些非靶向方法提供了迄今为止对碳氢化合物氧化产物最全面的分析，突出了原油光氧化产生的复杂混合物的多样性，以及针对分析充分监测环境中 HOP 的局限性。总之，这些数据确定了环境监测和溢油清理策略中的一个关键“盲点”，因为存在可能对人类和生态系统健康产生负面影响的大量 HOP。
