A binding phase based on the clay mineral montmorillonite (MT) was used as a sorbent in this work, which employed diffusive gradients in thin-film (DGT) devices to determine the lability of trace elements in natural waters. Montmorillonite exhibits low cost, wide availability, ease of handling, high ion-exchange capacity, and reusability. As(V), Ba2+, Cd2+, Co2+, Cr(III), Cu2+, Mn2+, Ni2+, Pb2+, Sr2+, V(V), and Zn2+ were quantitatively sorbed by MT and eluted with 1.0molL-1 HNO3, which provided efficiency above 70% of recovery. Validation tests were performed with synthetic solutions. The recovery of known concentrations ranged from 83 to 110%. The performance of modified DGT was compared with conventional DGT devices in experiments lasting 6 and 48h. The results obtained with both DGT devices showed no significant differences with 95% confidence. DGT samplers with MT were deployed in the determination of labile forms of the elements in water samples from Iguaçu River (Paraná, Brazil). The measured masses of elements in MT for various durations showed good fit to a theoretical line, indicating that the results agreed with the principle of the DGT technique. The concentrations of labile species in the sample proceeded as follows; Sr > Cd > Ba > Cu > Cr > Mn > Zn > Pb. The results suggest that DGT devices with MT are an effective alternative for speciation analysis of a wide range of elements (cations as well as anions) in natural waters.