We applied proton microbeam particle-induced X-ray emission (µ-PIXE) for mapping Ca, Zr, Ba and Yb, and atomic force microscopy (AFM) for imaging the surface landscape of a dental composite which releases Ca 2+ and F − for the protection of hard dental tissues. Three areas ∼250 × 250 µm 2 located ∼0.5-2 mm apart on a smooth surface specimen were mapped with 3.1 MeV protons focused to a ∼3.0 µm spot and at ∼3.9 µm pixel size sampling. The maps evidenced particles with diameters of 3.2-32 µm (Ca), 20-60 µm (Zr), ≤4 µm (Ba) and 10-50 µm (Yb). Cross-section area histograms of Ca-rich particles fitted with 2-6 Poisson functions revealed a polydisperse size distribution and substantial differences from an area to another, possibly implying large local variations of Ca 2+ released in the hard tissue near a dental filling of a few millimeters in diameter. Such imbalances may lead to low local Ca 2+ protection of the dental tissue, favoring the onset of secondary caries. Similarly, AFM images showed high zone-dependent differences in the distributions of grains with apparent diameters of 1-4 µm, plausibly recognized as Ca-and Ba-containing particles. In a simple model based on demineralization data, lateral diffusion of Ca 2+ between adjacent domains containing high-and low-area Ca-rich grains is described by exponential concentration gradients. These gradients may generate appreciable electromotive forces, which may enhance electrochemically the local tissue demineralization. Similar effects are to be expected in the protective action of F − ions released from microgranules of YbF 3 and of Ba fluoroaluminosilicate glass.