Simultaneously extracted metals (SEM) and acid volatile sulfide (AVS) show the potential for toxicity on the basis of their ratio. Accordingly, we spiked cadmium in a range for which Cd/AVS ratios were from 0.2 to 10 in the sediment with its weight about 8 kg in each batch. Dialysis samplers with a cation ion-exchange resin (Dowex 50W-X4) collection were used in a laboratory for the determination of free cadmium concentrations in pore water of the collected sediment. When equilibrium was reached among cadmium in pore water, sediment, and ion-exchange resin, cadmium exchanged onto resin phase was regenerated with 1 N hydrochloric acid (OPTIMA grade) and determined using an atomic absorption spectrophotometer (Zeeman 5000) with a graphite furnace accessory. Cadmium determined using the dialysis sampler is considered as free cadmium which is related to the metal bioavailability toward aquatic biota The developed methodology provides a new technique for assessment of free metal in aquatic sediment systems.