In order to predict metal bioavailability by microorganisms in natural waters, analytical speciation techniques such as the permeation liquid membrane (PLM) are required. A planar sheet PLM has been characterized by measuring Pb fluxes in the absence and presence of tiron and nitrilotriacetic, iminodiacetic, malonic, citric, polyacrylic and fulvic (Suwannee River fulvic, SRFA) acids. Important parameters such as the diffusion coefficient in the membrane phase and the effective distribution coefficient between the solution and membrane were evaluated in order to determine limiting conditions for the overall transport flux through the membrane. Subsequently, the PLM was tested for its ability to predict bioavailability by the freshwater alga, Chlorella kesslerii by comparing Pb PLM fluxes (J(PLM)) to Pb biouptake fluxes (J(int)) in the absence and presence of the synthetic ligands and SRFA. The capability of the PLM to mimic transport across biological membranes was demonstrated, in particular, from the similarity between the accumulated (PLM, algal) Pb vs. time plots under the different conditions. Under membrane transport limiting conditions, fluxes across both the PLM and biological membranes were proportional to the free metal ion and directly correlated to each other in the zone below saturation of the biological metal uptake sites. The correlation between the different fluxes may be used to predict Pb uptake by C. kesslerii in the presence of the synthetic ligands. However, in the presence of SRFA, the observed J(int) was much higher than predicted by results obtained either in the absence or presence of the synthetic ligands. (C) 2003 Elsevier B.V. All rights reserved.