Eco-friendly microextraction method for the quantitative speciation of 13 haloacetic acids in water

This paper describes the first micro liquid–liquid extraction (MLLE) gas chromatography–mass spectrometry (GC–MS) method for the speciation of emerging iodinated acetic acids, along with conventional chlorinated and brominated acids in water. The haloacetic acids (HAAs) were derivatised using 3 reagents for their methylation, both in aqueous and organic media. The acidic methanol derivatisation in aqueous medium provided the best efficiency, requiring minimal sample manipulation. The derivatisation yield was improved through the use of microwave energy that drastically reduced reaction time (2 min). The HAA methyl esters were finally extracted using 250 μL of methyl tert-butyl ether. This MLLE combined with the use of a large-volume sample injection coupled to a programmed temperature vaporiser–GC–MS improved the sensitivity of the method and minimised the generation of hazardous residues in accordance with the principles of “Green Chemistry”. Detection and quantification limits (excepting tribromoacetic acid) within the range of 0.01–0.15 μg/L and 0.03–0.5 μg/L, respectively, were obtained and the relative standard deviation was lower than 10%. The eco-friendly method was applied to the speciation of the 13 HAAs in treated (chlorinated and chloraminated water) and untreated water. Up to 8 HAAs were found at detectable levels in treated water. The highly toxic monoiodoacetic acid was detected in almost all the chloraminated water.