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Subsurface demineralization in enamel caries is known to entail diffusion of reagents and products both within the lesion and within the plaque biofilm external to the lesion. However, development of a predictive mathematical model for subsurface demineralization is hindered by limited quantitative understanding of the effects of these diffusion processes. The purpose of this quantitative study was to investigate and understand the effect of external diffusion length on the rate of demineralization in a simple model system. Ten, 500-μm thick sections cut from a porous hydroxyapatite (HAP) pellet were inserted in scanning microradiography (SMR) cells. The exposed thin edges of the sections were initially separated by columns of water (diffusion lengths) of 0–0.9 cm from a 1-l reservoir of demineralizing buffer (pH 4). Buffer was found to diffuse from the reservoir through the increasing diffusion lengths to the exposed HAP surface, whilst dissolved product diffused along the reverse path. Rates of HAP loss (from SMR measurements) decreased as the diffusion length increased. Experimental data were fitted to a general diffusion-reaction model. This showed that the solution near the HAP surface was almost completely saturated with HAP, and that the diffusion of dissolution products, rather than of buffer species, was rate limiting.