The objective of this research was to investigate the effects of matrix diffusion on solute transport in fractured volcanic tuff. Two tuff cores were studied, one with a matrix porosity of 0.27 and the other with a porosity of 0.14. The matrix permeabilities of the cores were 4.7¿10-15 and 7.8¿10-19 m2, 5 and 9 orders of magnitude less than the respective fracture permeabilities. This suggested that the cores could be modeled as dual-porosity systems with no flow in the matrix but significant solute storage capacity. Two types of tracer tests were conducted in each fractured core: (1) iodide was injected in separate experiments at different flow rates and (2) two tracers of different matrix diffusion coefficients (bromide and pentafluorobenzoate (PFBA)) were injected in another test. A difference in the maximum concentrations of the solutes and the extended tailing of the breakthrough curves were assumed to be indicative of diffusive mass transfer between the fracture and the porous matrix of the cores. Interpreting the results from both methods allowed the identification of matrix diffusion and dispersion effects within the fracture by simultaneously fitting the data sets (with known constraints) using a relatively simple conceptual model. Estimates of mass transfer coefficients for the fractured cores were also obtained. ¿ 2000 American Geophysical Union