A novel method for the retention of arsenate [As(V)] combining time-controlled solid-phase extraction with living bacterial biomass is presented. As(V) retention was carried out by exposing the extractant, consisting of a living double-mutant of Corynebacterium glutamicum strain ArsC1-C2, to the sample for a retention time of 1-7min, before the arsenic distribution equilibrium between the sample solution and the extractant was established. The amount of As(V) retained in the biomass was measured by inductively coupled plasma-mass spectrometry (ICP-MS) after the sample had been treated with nitric acid. A theoretical model of the retention process was developed to describe the experimental retention-time profiles obtained with the bacterial cells. This relationship provided a feasible quantification of the retention process before steady-state was reached, providing that the agitation conditions and the retention time had been controlled. An analytical procedure for the retention/quantification of As(V) was then developed; the detection limit was 0.1 ng As(V)mL(-1) and the relative standard deviation 2.4-3.0%. The maximum effective retention capacity for As(V) was about 12.5mgAs(g biomass)(-1). The developed procedure was applied to the determination of total arsenic in coal fly ash, using a sample that had undergone oxidative pre-treatment.