Electromembranes increase the efficiency of metal transport in liquid-phase microextraction systems by applying an electric potential, which accelerates the transport. Nevertheless, to get high extraction percentages in short extraction times it is necessary to take into account a great variety of factors, and multivariate optimization techniques are the best alternative to determine the most influential variables and to optimize the extraction process. In this work, a fractional factorial design was applied to determine the most influential variables in the extraction of silver by electromembranes. Thus, the effect of tri-isobutylphosphine sulphide (Cyanex 471x) concentration in the organic solution, sodium thiosulphate concentration in the acceptor solution, nitrate concentration in the sample solution, extraction time, stirring rate and electric potential on the enrichment factor were studied. Once the most important variables were selected, a small composite design (Draper-Lin) was used to obtain their optimal values to maximize the enrichment factor. Under these conditions, an experimental enrichment factor of 49.91 ± 3.95 was achieved after 22 min. Finally, the effect of saline matrix on the enrichment factor was tested and the optimized system was successfully applied to analyse silver concentrations at ultratrace levels, within the range of 7-29 ng·L-1 in different real seawater samples.
Keywords: Draper–Lin design; electromembranes; hollow-fibre liquid-phase microextraction; seawater; silver; tri-isobutylphosphine sulphide.