Rare earth elements (REEs) have been analysed from fossil vertebrate microremains (thelodont scales) from the Vesiku Bone Bed, Saaremaa, Estonia, using in situ microsampling by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Well-preserved scales of three species of the genus Thelodus (T. carinatus, T. laevis and Thelodus sp.) show very uniform REE patterns with slightly lower overall REE concentrations in enameloid than in dentine, with enrichment in middle REEs, depletion in heavy REEs and pronounced negative europium anomaly, but no cerium anomaly. The results of this study suggest a similar diagenetic history and possibly contemporaneous habitats for all three Thelodus species, as well as possible suboxic to anoxic conditions of the bottom and pore waters during the formation of the Vesiku Bone Bed.

Chemical signatures of carbonate biominerals are important for understanding biomineral formation, and are a subject of great interest in geosciences for applications in paleoclimatology and paleoceanography. A prominent unknown factor is the chemistry of organic matrices, in particular that of the inter-crystalline fraction. Here, we use atom probe tomography (APT) for the nanoscale chemical characterization of the mineral-organic interface in calcite from mussel shells. Our findings indicate that the quality of APT bulk chemistry results is highly dependent on sample preparation, yet data on biogenic calcite could be geochemically interpreted with confidence. Three-dimensional (3D) reconstructions of calcite tip specimens show the presence of organic matrix domains, characterized by the depletion of cations but enrichment in oxygen and carbon, and with at least 1% atomic increase in ¹⁶O relative to the surrounding mineral phase. This is the first relative, in-situ quantification of the chemical composition of the inter-crystalline organic matrix (IOM) for a carbonate biomineral, with implications for a better understanding of vital effects, proxy calibration, and the formation of these biocarbonates. Overall, our findings demonstrate the potential of nanoscale characterization of biominerals and their abiogenic counterparts to further advance our understanding of their chemistry.

A top-down approach to the mineralized structures and developmental steps that can be separated in the shells of Pinctada margaritifera was carried out. Detailed characterizations show that each of the two major layers usually taken into account (the outer prismatic layer and the inner nacreous layer) is actually the result of a complex process during which the microstructural patterns were progressively established. From its early growing stages in the deeper part of the periostracal grove up to the formation of the most inner nacreous layers, this species provides a demonstrative case study illustrating the leading role of specifically secreted organic structures as determinants of the crystallographic properties of the shell-building units. Gathering data established at various observational scales ranging from morphology to the nanometer level, this study allows for a reexamination of the recent and current biomineralization models.

Biominerals are important archives of the presence of life and environmental processes in the geological record. However, ascribing a clear biogenic nature to minerals with nanometer-sized dimensions has proven challenging. Identifying hallmark features of biologically controlled mineralization is particularly important for the case of magnetite crystals, resembling those produced by magnetotactic bacteria (MTB), which have been used as evidence of early prokaryotic life on Earth and in meteorites. We show here that magnetite produced by MTB displays a clear coupled C–N signal that is absent in abiogenic and/or biomimetic (protein-mediated) nanometer-sized magnetite. We attribute the presence of this signal to intracrystalline organic components associated with proteins involved in magnetosome formation by MTB. These results demonstrate that we can assign a biogenic origin to nanometer-sized magnetite crystals, and potentially other biominerals of similar dimensions, using unique geochemical signatures directly measured at the nanoscale. This finding is significant for searching for the earliest presence of life in the Earth’s geological record and prokaryotic life on other planets.