Migration of sharks into freshwater systems during the Miocene and implications for Alpine paleoelevation

Trace-element and isotopic compositions of fossilized shark teeth sampled from Miocene marine sediments of the north Alpine Molasse Basin, the Vienna Basin, and the Pannonian Basin generally show evidence of formation in a marine environment under conditions geochemically equivalent to the open ocean. In contrast, two of eight shark teeth from the Swiss Upper Marine Molasse locality of La Moliere have extremely low delta O-18 values (10.3% and 11.3%) and low Sr-87/Sr-86 ratios (0.707840 and 0.707812) compared to other teeth from this locality (21.1%,22.4%o and 0.708421-0.708630). The rare earth element (REE) abundances and patterns from La Moliere not only differ between dentine and enameloid of the same tooth, but also between different teeth, supporting variable conditions of diagenesis at this site. However, the REE patterns of enameloid from the ``exotic'' teeth analyzed for O and Sr isotopic compositions are similar to those of teeth that have O and Sr isotopic compositions typical of a marine setting at this site. Collectively, this suggests that the two ``exotic'' teeth were formed while the sharks frequented a freshwater environment with very low O-18-content and Sr isotopic composition controlled by Mesozoic calcareous rocks. This is consistent with a paleogeography of high-elevation (similar to 2300 m) Miocene Alps adjacent to a marginal sea.

Early diagenesis of bone and tooth apatite in fluvial and marine settings: Constraints from combined oxygen isotope, nitrogen and REE analysis

Fossil bones and teeth of Late Pleistocene terrestrial mammals from Rhine River gravels (RS) and the North Sea (NS), that have been exposed to chemically and isotopically distinct diagenetic fluids (fresh water versus seawater), were investigated to study the effects of early diagenesis on biogenic apatite. Changes in phosphate oxygen isotopic composition (delta O-18(PO4)), nitrogen content (wt.% N) and rare earth element (REE) concentrations were measured along profiles within bones that have not been completely fossilized, and in skeletal tissues (bone, dentine, enamel) with different susceptibilities to diagenetic alteration. Early diagenetic changes of elemental and isotopic compositions of apatite in fossil bone are related to the loss of the stabilizing collagen matrix. The REE concentration is negatively correlated with the nitrogen content, and therefore the amount of collagen provides a sensitive proxy for early diagenetic alteration. REE patterns of RS and NS bones indicate initial fossilization in a fresh water fluid with similar REE compositions. Bones from both settings have nearly collagen-free, REE-, U-, F- and Sr-enriched altered outer rims, while the collagen-bearing bone compacta in the central part often display early diagenetic pyrite void-fillings. However, NS bones exposed to Holocene seawater have outer rim delta O-18(PO4) values that are 1.1 to 2.6 parts per thousand higher compared to the central part of the same bones (delta O-18(PO4) = 18.2 +/- 0.9 parts per thousand, n = 19). Surprisingly, even the collagen-rich bone compacta with low REE contents and apatite crystallinity seems altered, as NS tooth enamel (delta O-18(PO4) =15.0 +/- 0.3 parts per thousand, n=4) has about 3%. lower delta O-18(PO4) values, values that are also similar to those of enamel from RS teeth. Therefore, REE concentration, N content and apatite crystallinity are in this case only poor proxies for the alteration of delta O-18(PO4) values. Seawater exposure of a few years up to 8 kyr can change the delta O-18(PO4) values of the bone apatite by > 3 parts per thousand. Therefore, bones fossilized in marine settings must be treated with caution for palaeoclimatic reconstructions. However, enamel seems to preserve pristine delta O-18(PO4) values on this time scale. Using species-specific calibrations for modern mammals, a mean delta O-18(H2O) value can be reconstructed for Late Pleistocene mammalian drinking water of around -9.2 +/- 0.5 parts per thousand, which is similar to that of Late Pleistocene groundwater from central Europe. (c) 2008 Elsevier B.V. All rights reserved.