Spatial distribution of trace element Ca-normalized ratios in primary and permanent human tooth enamel

•A comprehensive framework of the distribution of some trace elements in tooth enamel is proposed.•Ca-normalized ratios of Cu, Ni, Zn, Sr and Ba discriminate deciduous \and permanent teeth.•It is recommended to perform laser ablation rasters along the dentine-enamel junction.•The transfer of these elements to human enamel is discussed.

The trace elements distribution embedded in tooth enamel offers a means to study exposure of toxic metals and allows the reconstruction of dietary behaviors. The quantification of most of the elements with a spatial high resolution (~ 50 μm) is routinely achieved using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). However, the lack of a comprehensive framework of trace elements distribution in enamel jeopardizes any endorsed sampling strategy using LA-ICPMS. The present work is an effort to improve our knowledge on this issue. We studied a suite of 22 sectioned teeth with known dietary history, including 12 3rd molars from 12 living individuals and 10 primary teeth from 3 living individuals. Using LA-ICPMS, we measured Ca, Cu, Zn, Ni, Sr, Ba and Pb variations along 2 or 3 rasters from cervical to occlusal enamel. Calcium concentrations are lower in primary than in permanent teeth and do not vary spatially within a tooth suggesting that enamel matures homogeneously before eruption. The Pb/Ca ratio does not vary within tooth enamel and between primary and permanent tooth enamel. The Cu/Ca and Ni/Ca ratios do not vary within tooth enamel but discriminate primary from permanent tooth enamel. The Zn/Ca ratios are higher in permanent than in primary tooth enamel, and increase up to an order of magnitude in the last hundred of microns at the enamel surface. The Sr/Ca and Ba/Ca ratios are higher in permanent than in primary tooth enamel, and decrease from the enamel-dentine junction towards outer enamel in permanent but not in primary tooth enamel. Considering the Ca-normalized intra-tooth variations of Zn, Sr and Ba, we recommend to perform laser ablation rasters along the enamel-dentine junction because this area is likely to retain most of the original and complete chemical information related to individual's life.

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