Abstract
Electromembrane extraction (EME) was used as an off‐line sample pre‐treatment method for the determination of heavy metal cations in aqueous samples using CE with capacitively coupled contactless conductivity detection (CE‐C^4^D). A short segment of porous polypropylene hollow fibre was penetrated with 1‐octanol and 0.5% v/v bis(2‐ethylhexyl)phosphonic acid and constituted a low cost, single use, disposable supported liquid membrane, which selectively transported and pre‐concentrated heavy metal cations into the fibre lumen filled with 100 mM acetic acid acceptor solution. Donor solutions were standard solutions and real samples dissolved in deionized water at neutral pH. At optimized EME conditions (penetration time, 5 s; applied voltage, 75 V; and stirring rate, 750 rpm), 15–42% recoveries of heavy metal cations were achieved for a 5 min extraction time. Repeatability of the EME pre‐treatment was examined for six independent EME runs and ranged from 6.6 to 11.1%. Limits of detection for the EME‐CE‐C^4^D method ranged from 25 to 200 nM, resulting into one to two orders of magnitude improvement compared with CE‐C^4^D without sample treatment. The developed EME sample pre‐treatment procedure was applied to the analysis of heavy metal cations in tap water and powdered milk samples. Zinc in the real samples was identified and quantified in a background electrolyte solution consisting of 20 mM L‐histidine and 30 mM acetic acid at pH 4.95 in about 3 min.