In‐line preconcentration capillary zone electrophoresis for the analysis of haloacetic acids in water

Two in‐line enrichment procedures (large volume sample stacking (LVSS) and field amplified sample injection (FASI)) have been evaluated for the CZE analysis of haloacetic acids (HAAs) in drinking water. For LVSS, separation on normal polarity using 20 mM acetic acid–ammonium acetate (pH 5.5) containing 20% ACN as BGE was required. For FASI, the optimum conditions were 25 s hydrodynamic injection (3.5 kPa) of a water plug followed by 25 s electrokinetic injection (?10 kV) of the sample, and 200 mM formic acid–ammonium formate buffer at pH 3.0 as BGE. For both FASI and LVSS methods, linear calibration curves (r²>0.992), limit of detection on standards prepared in Milli‐Q water (49.1–200 μg/L for LVSS and 4.2–48 μg/L for FASI), and both run‐to‐run and day‐to‐day precisions (RSD values up to 15.8% for concentration) were established. Due to the higher sensitive enhancement (up to 310‐fold) achieved with FASI‐CZE, this method was selected for the analysis of HAAs in drinking water. However, for an optimal FASI application sample salinity was removed by SPE using Oasis WAX cartridges. With SPE‐FASI‐CZE, method detection limits in the range 0.05–0.8 μg/L were obtained, with recoveries, in general, higher than 90% (around 65% for monochloroacetic and monobromoacetic acids). The applicability of the SPE‐FASI‐CZE method was evaluated by analyzing drinking tap water from Barcelona where seven HAAs were found at concentration levels between 3 and 13 μg/L.