Atmospheric pressure gas chromatography–time-of-flight-mass spectrometry (APGC–ToF-MS) for the determination of regulated and emerging contaminants in aqueous samples after stir bar sorptive extraction (SBSE)

•102 regulated and emerging contaminants are simultaneously extracted by SBSE.•APGC–ToF-MS is presented as an alternative to EI for the analysis of microcontaminants.•Identification of non-target compounds in environmental matrices is also explored.

This work presents the development, optimization and validation of a multi-residue method for the simultaneous determination of 102 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and several types of pesticides in aqueous matrices. Water samples were processed using stir bar sorptive extraction (SBSE) after the optimization of several parameters: agitation time, ionic strength, presence of organic modifiers, pH, and volume of the derivatizing agent. Target compounds were extracted from the bars by liquid desorption (LD). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to time-of-flight (ToF-MS) mass spectrometry. A new ionization source, atmospheric pressure gas chromatography (APGC), was tested. The optimized protocol showed acceptable recovery percentages (50–100%) and limits of detection below 1 ng L−1 for most of the compounds. Occurrence of 21 out of 102 analytes was confirmed in several environmental aquatic matrices, including seawater, sewage effluent, river water and groundwater. Non-target compounds such as organophosphorus flame retardants were also identified in real samples by accurate mass measurement of their molecular ions using GC-APGC–ToF-MS. To the best of our knowledge, this is the first time that this technique has been applied for the analysis of contaminants in aquatic systems. By employing lower energy than the more widely used electron impact ionization (EI), AGPC provides significant advantages over EI for those substances very susceptible to high fragmentation (e.g., fragrances, pyrethroids).

Graphical abstractExamples of identification of target (triclosan, TCS) and non-target (tributhyl phosphate, TBP) compounds in environmental water samples by APGC–ToF-MS. Some confirmation criteria are shown (i.e. mass spectra, isotopic distribution, and accurate mass).Figure optionsDownload full-size imageDownload as PowerPoint slide