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Schlagwörter:
Bone fossilization
Oxygen isotope composition
Raman spectroscopy
Secondary ion mass spectrometry
Isotope ratio infrared spectroscopy
Zusammenfassung:
Bones and teeth are often the only fossil remains of vertebrates that are preserved over geological time in sedimentary rocks. They render valuable archives for geochemical proxies which are commonly used for paleo-reconstructions. However, the fossilization mechanisms of bone are not yet well understood. Crucial processes are the transformation of bioapatite and the replacement of collagen by thermodynamically more stable apatite phases, such as fluorapatite. In the present study, aqueous alteration experiments on cortical bone samples were performed under simulated early diagenetic conditions in order to investigate whether and how an external PO4 source affects post mortem bone mineralization. Additionally, abiotic oxygen isotope exchange mechanisms between bioapatite and aqueous solutions were assessed by using either 18O-enriched water or phosphate as a tracer. The presence of an external sedimentary 18O-labeled PO4 source led to a rapid formation of new fluorapatite crystallites at the sample’s margin that was highly enriched in 18O. Meanwhile, in the interior of the samples carbonate-poor HAp formed through a dissolution-precipitation process without incorporating any of the 18O tracer. These two processes appear to act independently from each other. In samples exposed to 18O-labeled aqueous solutions lacking a PO4 source, no newly grown apatite crystallites were found, however in the interior of these samples, nano-crystalline carbonate-poor or -free hydroxylapatite precipitated. A comparatively low but uniform 18O-enrichment was measured from the sample’s margin towards its interior, which is assumed to have resulted from the adsorption of H218O onto crystallite surface sites and collagen. Overall, our results suggest that a fast incorporation of 18O-doped PO4 from the sediment source accelerated bone mineralization and consequently changed the oxygen isotope composition of the PO4 group in the bone mineral phase more rapidly and to a greater extent than in a diagenetic setting lacking additional external PO4. Dissolved phosphate from the taphonomic setting thus seems to be an important factor fostering bone fossilization and preservation as well as oxygen isotope alteration.
