Diagenesis has been recognized for decades to significantly alter the trace elements biogenic signatures in fossil tooth enamel and bone that are routinely used for paleobiological and paleoenvironmental reconstructions. This signature is modified during diagenesis according to a complex continuum between two main processes, addition and substitution. For an additive-like, or early diagenesis, the trace elements biogenic profiles can be restored by leaching secondary minerals, but this technique is inefficient for a substitutive-like, or extensive diagenesis for which secondary trace elements are incorporated into the biogenic mineral. This scheme is however unclear for Ca, the major cation in tooth enamel and bone hydroxylapatite, whose stable isotope composition (δ44/42Ca) also conveys biological and environmental information. We present a suite of leaching experiments for monitoring δ44/42Ca values in artificial and natural fossil enamel and bone from different settings. The results show that enamel δ44/42Ca values are insensitive to an additive-like diagenesis that involves the formation of secondary Ca- carbonate mineral phases, while bone shows a consistent offset toward 44Ca-enriched values, that can be restored to the biogenic baseline by a leaching procedure. In the context of a substitutive-like diagenesis, bone exhibits constant δ44/42Ca values, insensitive to leaching, and shows a REE pattern symptomatic of extensive diagenesis. Such a REE pattern can be observed in fossil enamel for which δ44/42Ca values are still fluctuating and follow a trophic pattern. We conclude that Ca isotopes in fossil enamel are probably not prone to extensive diagenesis and argue that this immunity is due to the very low porosity of enamel that cannot accommodate enough secondary minerals to significantly modify the isotopic composition of the enamel Ca pool.
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RBINS Staff Publications 2023
The upper part of the Kortrijk Clay Formation (the Roubaix Clay and Aalbeke Clay Members of mid-Ypresian age) has been exposed in road and canal cuttings and clay quarries in the Kortrijk area (western Belgium), and penetrated by several cored boreholes. It is overlain disconformably by the Mont-Panisel Sand Member of the Hyon Sand Formation (upper middle Ypresian). The Roubaix Clay Member contains diverse and well-preserved calcareous nannofossils, dinoflagellate cysts, foraminifera, ostracods and other calcitic microfossils, and less well-preserved mollusc assemblages, while the Aalbeke Clay Member is secondarily decalcified. The calcareous nannofossil subdivision of upper NP11 and lower NP12 has been recognised in the Kortrijk area, and calibrated with the NW European mid-Ypresian dinoflagellate cyst, ostracod and planktonic foraminiferal zones and datums (e.g. Subbotina influx). Several medium-scale depositional sequences, with an estimated duration of 400 kyr or less, have been recorded. Their respective boundaries coincide with the resistivity maxima identified on the majority of the wireline log profiles of the Belgian Ypresian. Integrated biostratigraphic, magnetostratigraphic and sequence stratigraphic analysis enables correlation with other areas in Belgium, with the London Clay Formation of southern England, and with the standard chronostratigraphic scale. A marine erosion surface has been identified at the base of Unit 20 in the Kortrijk area (mid-Ypresian, early Biochron NP12, middle C24n.1n, ~ 52.8 Ma), corresponding to the first occurrence of estuarine channel-fill units in southern England. This indicates a brief but profound sea-level fall, either eustatically or tectonically controlled. The composite Kortrijk section is proposed as a reference section for the middle Ypresian in the southern North Sea Basin, and for similar settings in mid- to high-latitudes of the Northern Hemisphere (e.g. Kazakhstan and Crimea).
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RBINS Staff Publications 2017
