Static headspace gas chromatography–mass spectrometry for the one-step derivatisation and extraction of eleven aldehydes in drinking water

• The first HS–GC–MS method for the simultaneous derivatisation, extraction and quantification of 11 low-molecular-mass aldehydes (LMMAs) is proposed.
• The derivatisation reaction with PFBHA is carried out at alkaline pH.
• Sodium hydrogen carbonate enhances the derivatisation efficiency of the LMMAs up to 20-fold.
• The process of derivatisation and extraction of LMMAs is accomplished in 20 min at 80 °C.

Low-molecular-mass aldehydes (LMMAs) are water disinfection by-products formed by the reaction of ozone and/or chlorine with natural organic matter in water. LMMAs are mutagenic and carcinogenic compounds, which are detected at ng/L levels in water. An analytical method that allows simultaneous derivatisation and extraction of LMMAs in water has been developed using the classical static headspace technique coupled with gas chromatography–mass spectrometry (HS–GC–MS). Important parameters controlling the derivatisation of LMMAs with o-2,3,4,5,6-pentafluorobenzylhydroxylamine, oxime-products extraction and headspace generation were optimised to obtain the highest sensitivity, completing the entire process in 20 min. For the first time the derivatisation reaction was carried out at alkaline pH adjusted with sodium hydrogen carbonate which exerts a significant enhancement effect on the derivatisation efficiency of the aldehydes; up to 20-fold with respect to those obtained in weak acid media as recommended by EPA Method 556.1. The addition of 200 μL of n-hexane, as a chemical modifier, favoured the volatilisation of oxime-products, increasing the sensitivity of the method. The proposed method allows the achieving of detection limits from 2 to 80 ng/L and has excellent precision (RSD average value of 6.4%) and accuracy (recovery ranging from 97% to 99%) for LMMA quantifications in drinking water samples. Finally, the HS–GC–MS method was validated relative to EPA Method 556.1 for the analysis of drinking water samples subjected to several disinfection treatments.