The diffusivity and diffusion mechanisms of hydrogen together with with deuterium and lithium, parallel to the c axis of quartz, were investigated experimentally at 800 degrees C, 0.1 GPa with the activity of H2O or (H2O)-H-2 approximate to 1 [H-2 is used throughout this work to describe deuterium rather than D, to avoid confusion with the diffusion coefficient, D]. The pH was set using mixtures of H2O (or (H2O)-H-2) and HCl. Three types of experiment were conducted: (1) H-in/Li-out; (2) H-2-in/H-out; and (3) H-2-in/H + Li out, using three different natural quartz crystals as starting materials. Profiles of H, H-2 and Li were measured using Fourier-transform infrared (FTIR) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). H, H-2 and Li are charge-compensated by Al3+ replacing Si4+, or by excess O2-. The total atomic concentration of monovalent cations appears to remain constant over the duration of the experiments. The resulting diffusion profiles are different for the three experimental designs and three starting materials, and some show complex shapes inconsistent with simple diffusion. A multi-site diffusion-reaction model is developed, with the theory based on previous models that have been derived mainly on the basis of conductivity measurements. In these models, the monovalent cations move away from their charge-balancing ion then diffuse rapidly to another site. The mobility of the monovalent cations is described by both a diffusion coefficient and an equilibrium constant that enables dissociation of the immobile charge-balanced defects. This model can describe complex step-shaped profiles formed in H-in/Li-out experiments, profiles with local maxima ('humped' profiles) in H-2-in/H + Li out experiments, and error function-shaped profiles in H-2-in/H-out and previously published Li-in/H-out experiments. Our data provide support for models previously proposed for quartz. Studies of the lengths and forms of diffusion profiles from such experiments provide a useful complement to assertions from conductivity experiments., Mineralogical Magazine, 86 (1)