Assessment of styrene‐divinylbenzene polymer (PPL) solid‐phase extraction and non‐targeted tandem mass spectrometry for the analysis of xenobiotics in seawater

Abstract

AbstractAnthropogenic imprints have become a fundamental part of most ecosystems. Our chemical footprint is often detected using targeted approaches, whereas xenobiotics are embedded within the large pool of dissolved metabolites, altered by biotic and abiotic mechanisms. Thus, it is necessary to simultaneously study anthropogenic signals entwined with the variety of organic signatures that exist in aquatic environments. However, methods for non‐targeted analysis of natural metabolites are not always well suited for the analysis of pollutants. Here, we report the reassessment of styrene‐divinylbenzene polymer‐based Priority PolLutant (PPL) solid‐phase extraction (PPL‐SPE), which is typically used to extract marine dissolved organic matter (DOM) for biogeochemical studies, to analyze a set of xenobiotics commonly observed in coastal North Pacific seawater. After PPL extraction and analysis by nontargeted liquid chromatography tandem mass spectrometry (LC–MS/MS), we successfully detected 23 out of 25 selected pharmaceuticals, personal care products, biocides, perfluorocarbons, and polymer additives in a complex marine DOM sample using positive and negative electrospray ionization. We tested two pH conditions to mimic typical marine DOM extraction studies and found mean recovery rates of xenobiotics were approximately 10% higher in seawater pH (pH ~ 8) than in acidified samples (pH ~ 2) for both negative and positive modes, although overall, mean recovery rates were 10% lower in negative mode. Our results indicate that PPL‐SPE in combination with non‐targeted LC–MS/MS is capable of capturing the tested set of xenobiotics, thus allowing the repurposing of biogeochemical sampling strategies as well as existing DOM samples and MS data for the subsequent assessment of anthropogenic impacts in marine environments.