Untreated urban stormwater runoff contributes to poor water quality in receiving waters. The ability to identify toxicants and other bioactive molecules responsible for observed adverse effects in a complex mixture of contaminants is critical to effective protection of ecosystem and human health, yet this is a challenging analytical task. The objective of this study was to develop analytical methods using liquid chromatography coupled to high-resolution quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) to detect organic contaminants in highway runoff and in runoff-exposed fish (adult coho salmon, Oncorhynchus kisutch). Processing of paired water and tissue samples facilitated contaminant prioritization and aided investigation of chemical bioavailability and uptake processes. Simple, minimal processing effort solid phase extraction (SPE) and elution procedures were optimized for water samples, and selective pressurized liquid extraction (SPLE) procedures were optimized for fish tissues. Extraction methods were compared by detection of non-target features and target compounds (e.g., quantity and peak area), while minimizing matrix interferences. Suspect screening techniques utilized in-house and commercial databases to prioritize high-risk detections for subsequent MS/MS characterization and identification efforts. Presumptive annotations were also screened with an in-house linear regression (logK_owvs. retention time) to exclude isobaric compounds. Examples of confirmed identifications (via reference standard comparison) in highway runoff include ethoprophos, prometon, DEET, caffeine, cotinine, 4(or 5)-methyl-1H-methylbenzotriazole, and acetanilide. Acetanilide was also detected in runoff-exposed fish gill and liver samples. Further characterization of highway runoff and fish tissues (14 and 19 compounds, respectively with tentative identification by MS/MS data) suggests that many novel or poorly characterized organic contaminants exist in urban stormwater runoff and exposed biota.

中文翻译：

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高分辨率飞行时间质谱技术开发可疑和非目标的筛查方法，用于检测公路径流和鱼类组织中的有机污染物

未经处理的城市雨水径流导致接收水的水质差。在复杂的污染物混合物中识别导致观察到的不良影响的有毒物质和其他生物活性分子的能力，对于有效保护生态系统和人类健康至关重要，但这是一项艰巨的分析任务。这项研究的目的是开发使用液相色谱结合高分辨率四极杆飞行时间质谱（LC-QTOF-MS）的分析方法，以检测高速公路径流和径流暴露的鱼类（成年鲑）中的有机污染物。 ，Oncorhynchus kisutch）。配对的水和组织样品的处理有助于确定污染物的优先级，并有助于研究化学生物利用度和吸收过程。简单，最少的处理工作针对水样品优化了固相萃取（SPE）和洗脱程序，针对鱼组织优化了选择性加压液体萃取（SPLE）程序。通过检测非目标特征和目标化合物（例如数量和峰面积）来比较提取方法，同时最大程度地减少基质干扰。可疑筛查技术利用内部和商业数据库来优先进行高风险检测，以进行后续的MS / MS表征和鉴定工作。还使用内部线性回归筛选假设性注释（log K_流量与保留时间之比）以排除同量异位化合物。公路径流中经确认的鉴定（通过参考标准比较）的例子包括乙草胺，普罗姆顿，DEET，咖啡因，可替宁，4（或5）-甲基-1 H-甲基苯并三唑和对乙酰苯胺。在径流暴露的鱼g和肝脏样品中也检出了乙酰苯胺。公路径流和鱼类组织的进一步表征（分别由MS / MS数据初步鉴定的14和19种化合物）表明，城市雨水径流和裸露的生物区系中存在许多新颖的或表征较差的有机污染物。