Improving methodological aspects of the analysis of five regulated haloacetic acids in water samples by solid-phase extraction, ion-pair liquid chromatography and electrospray tandem mass spectrometry

Haloacetic acids (HAAs) are organic pollutants originated from the drinking water disinfection process, which ought to be controlled and minimized. In this work a method for monitoring haloacetic acids (HAAs) in water samples is proposed, which can be used in quality control laboratories using the techniques most frequently available. Among its main advantages we may highlight its automated character, including minimal steps of sample preparation, and above all, its improved selectivity and sensitivity in the analysis of real samples. Five haloacetic acids (HAA5) were analyzed using solid-phase extraction (SPE) combined with ion-pair liquid chromatography and tandem mass spectrometry. For the optimization of the chromatographic separation, two amines (triethylamine, TEA and dibutylamine, DBA) as ion pair reagents were compared, and a better selectivity and sensitivity was obtained using DBA, especially for monohaloacetic acids. SPE conditions were optimized using different polymeric adsorbents.The electrospray source parameters were studied for maximum precursor ion accumulation, while the collision cell energy of the triple quadrupole mass spectrometer was adjusted for optimum fragmentation. Precursor ions detected were deprotonated, dimeric and decarboxylated ions. The major product ions formed were: ionized halogen atom (chloride and bromide) and decarboxylated ions. After enrichment of the HAAs in Lichrolut EN adsorbent, the limits of detection obtained by LC–MS/MS analysis (between 0.04 and 0.3 ng mL−1) were comparable to those obtained by GC–MS after derivatization. Linearity with good correlation coefficients was obtained over two orders of magnitude irrespective of the compound. Adequate recoveries were achieved (60–102%), and the repeatability and intermediate precision were in the range of 2.4–6.6% and 3.8–14.8%, respectively. In order to demonstrate the usefulness of the method for routine HAAs monitoring, different types of water samples were analyzed. In swimming pool water samples the ∑HAAs were determined between 76 and 154 ng mL−1.

► Superior selectivity in HAA determination using ion-pair liquid chromatography.
► Improved sensitivity in HAAs analysis using tandem mass spectrometry.
► Enhanced extraction efficiency using Lichrolut polymeric solid-phase adsorbent and elution with ion-pair reagent.
► Preliminary results of HAAs in drinking water and particularly swimming pool water.