The increasing use of natural unsaturated zones as repositories for landfills and disposal sites for hazardous wastes (chemical and radioactive) requires a greater understanding of transport processes in the unsaturated zone. For volatile constituents an important potential transport mechanism is gaseous diffusion. Diffusion, however, cannot be treated as an independent isolated transport mechanism. A complete understanding of multicomponent gas transport in porous media (unsaturated zones) requires a knowledge of Knudsen transport, the molecular and nonequimolar components of diffusive flux, and viscous (pressure driven) flux. The constitutive equations relating these flux components are available from the “dusty gas” model of Mason et al. (1967). This review presents a brief discussion of the underlying principles and interrelationships among each of the above flux mechanisms. Some aspects of these transport mechanisms are, to our knowledge, generally unrecognized in the Earth science literature. The principles underlying the transport mechanisms are illustrated with binary systems; the constitutive equations are then cast in forms thought to be most useful for the study of natural unsaturated zones. The viscous and diffusive fluxes are coupled in the constitutive equations through the Knudsen diffusivities; a knowledge of Knudsen diffusivities is necessary to calculate the viscous component of flux and pressure gradients. The Knudsen diffusivities can be calculated from measurements of the Klinkenberg effect. Two examples are presented showing that in natural systems, very small pressure gradients (1 Pa/m or less) can produce viscous fluxes greater than or equal to diffusive fluxes and that, conversely, pressure gradients of this magnitude can be generated by diffusive processes. The example calculations show that major concentration gradients can be developed for stagnant (zero flux, nonreactive) gases. A method is presented for approximating the viscous and diffusive flux components of gases in a multicomponent system from a knowledge of the concentration profiles of stagnant gases. In subsoil environments, argon and nitrogen are considered to be stagnant gases. Fick's laws are essentially, by definition, inadequate to deal with stagnant gases. In the examples presented, the error associated with estimating the total fluxes of nonstagnant gases by Fick's law, relative to stationary coordinates, ranges from a few percent to orders of magnit