Quantification of volatile-alkylated selenium and sulfur in complex aqueous media using solid-phase microextraction

•Extraction of volatile-alkylated Se and S compounds from complex aqueous media.•Simultaneous analysis of 10 volatile-alkylated Se and S compounds in the ng/L range.•Thorough evaluation of sample matrix effects.•Assessment of potential analyte transformations during sample storage.•Application of method on (incubated) raw wastewater and natural surface water.

Biologically produced volatile-alkylated Se and S compounds play an important role in the global biogeochemical Se and S cycles, are important constituents of odorous industrial emissions, and contribute to (off-)flavors in food and beverages. This study presents a fully automated direct-immersion solid-phase microextraction (DI-SPME) method coupled with capillary gas chromatography−mass spectrometry (GC/MS) for the simultaneous quantification of 10 volatile-alkylated Se and S compounds in complex aqueous media. Instrumental parameters of the SPME procedure were optimized to yield extraction efficiencies of up to 96% from complex aqueous matrices. The effects of sample matrix composition and analyte transformation during sample storage were critically assessed. With the use of internal standards and procedural calibrations, the DI-SPME−GC/MS method allows for trace-level quantification of volatile Se and S compounds in the ng/L range (e.g. down to 30 ng/L dimethyl sulfide and 75 ng/L dimethyl selenide). The applicability and robustness of the presented method demonstrate that the method may be used to quantify volatile Se and S compounds in complex aqueous samples, such as industrial effluents or food and beverage samples.