Quantification of organic contaminants in urban stormwater by isotope dilution and liquid chromatography-tandem mass spectrometry
Pollutants transported in urban stormwater runoff induce pervasive water quality degradation in receiving waters. To accurately characterize stormwater quality and treatment system performance across the range of possible contaminant characteristics, comprehensive multi-residue analytical methods are necessary. Here, we developed a solid-phase extraction (SPE) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method to quantify representative stormwater-derived organic contaminants across multiple chemical classes, including vehicle-related chemicals, corrosion inhibitors, industrial chemicals, pesticides, pharmaceuticals and personal care products, and antioxidants. Extraction conditions, isotope-labeled internal standards, and LC-MS/MS parameters were optimized to enhance recovery, minimize matrix effects, and maximize selectivity and sensitivity. The developed method was sensitive (method quantification limits < 10 ng/L for > 80% of selected analytes) and accurate (mean relative recoveries in the range of 70–130%, with relative standard deviations < 25% for 77% of the analytes) for most of the analytes. The method was used to analyze samples collected from nine urban watersheds during a storm event; 62% of the 39 analytes were detected at least once at concentrations up to 540 ng/L (1,3-diphenylguanidine). Spatial trends in detection and concentration were observed for vehicle-related and industrial chemicals that correlated with vehicle traffic. Total concentrations of pesticides suggested that residential uses could be more important sources than agriculture. This study illustrates the pervasive occurrence of a wide variety of stormwater-derived chemicals in urban receiving waters and highlights the need to better understand their environmental fate and ecological implications.
KeywordsStormwater runoff Organic contaminants Liquid chromatography-tandem mass spectrometry Multi-class analysis Isotope-labeled internal standards Spatial trend
The research group at the Center for Urban Waters and the University of Washington (Tacoma and Seattle campuses) is greatly appreciated for helping with the experiments, data analysis, and manuscript writing. We thank Agilent for their excellent technical advice.
This work was partially supported by the Environmental Protection Agency (EPA grant no. 01J18101) and the University of Washington (Tacoma/Seattle). Fan Hou received scholarship support from the Chinese Scholarship Council for her visit to the Department of Civil and Environmental Engineering (UW-Seattle) as a joint Ph.D. student.
Compliance with ethical standards
This article does not contain any studies with human or animal subjects.
Conflict of interest
The authors declare that they have no conflict of interest.
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