Multiresidue analysis of pollutants as their trimethylsilyl derivatives, by gas chromatography–mass spectrometry

This paper reports a multiresidue analysis procedure which permits the identification and quantification of sixty-three water-soluble pollutants. Subsequent to their solid-phase extraction (SPE) enrichment, analyses of species have been carried out from one solution, by a single injection, as their trimethylsilyl-oxime ether/ester derivatives, by gas chromatography–mass spectrometry, within 31 min. Based on our optimized extraction, derivatization and mass fragmentation studies separation have been performed in the total ion current mode, identification and quantification of compounds have been carried out on the basis of their selective fragment ions. Including various pharmaceuticals, benzoic acid, its substituted species, different aromatic carboxylic acids, cholic acids, unsaturated and saturated fatty acids, aliphatic dicarboxylic acids, as well as synthetic pollutants of various origins (2,4-di-tert-butylphenol, different phthalates). Standard compounds were added to 500 mL effluent wastewater samples, at three concentrations (1–5 μg/L, 5–10 μg/L and 10–20 μg/L). Recoveries, using the Waters Oasis cartridges performing extractions at pH 2, pH 4 and pH 7 proved to be the optimum at pH 4 (average recoveries (94.5%), except for cholesterol (10%), paracetamol (18%) and 2,5-dihydroxybenzoic acid (25%). Carbamazepine could be recovered at pH 7, only. Responses, obtained with derivatized standards proved to be linear in the range of 4–80 μg/L levels. Limit of quantitation values varied between 0.92 ng/L (4-hydroxyphenylacetic acid) and 600 ng/L (dehydrocholic acid) concentrations. One of the most important messages of this work is the confirmation of the origin of blank values. It was shown that contaminants, mainly 2,4-di-tert-butylphenol, different phthalates and fatty acids, are sourced both from the reagents and mainly from the SPE procedure, independent on the cartridge applied. Reproducibilities, characterized with the relative standard deviations (RSDs) of measurements, varied between 0.71% and 10%, with an average of 4.38% RSD. The practical utility of the method was shown by the identification and quantification of the pollutant contents of Hungarian influent and effluent wastewaters (for six consecutive months and that of the Danube River for 2 months).