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NON-AVIAN DINOSAUR EGGSHELL CALCITE CONTAINS ANCIENT, ENDOGENOUS AMINO ACIDS

View ORCID ProfileEvan T. Saitta, Jakob Vinther, Molly K. Crisp, Geoffrey D. Abbott, Thomas G. Kaye, Michael Pittman, Ian Bull, Ian Fletcher, Xinqi Chen, Matthew J. Collins, Jorune Sakalauskaite, Meaghan Mackie, Federica Dal Bello, Marc R. Dickinson, Mark A. Stevenson, Paul Donohoe, Philipp R. Heck, Beatrice Demarchi, Kirsty E. H. Penkman
doi: https://doi.org/10.1101/2020.06.02.129999
Evan T. Saitta
1Integrative Research Center, Field Museum of Natural History, Chicago, Illinois, USA
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  • For correspondence: evansaitta@gmail.com
Jakob Vinther
2School of Earth Sciences, University of Bristol, Bristol, UK
3School of Biological Sciences, University of Bristol, Bristol, UK
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Molly K. Crisp
4Department of Chemistry, University of York, York, UK
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Geoffrey D. Abbott
5School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne, UK
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Thomas G. Kaye
6Foundation for Scientific Advancement, Sierra Vista, Arizona, USA
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Michael Pittman
7Vertebrate Palaeontology Laboratory, Department of Earth Sciences, The University of Hong Kong, Pokfulam, Hong Kong, China
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Ian Bull
8School of Chemistry, University of Bristol, Bristol, UK
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Ian Fletcher
9Faculty of Engineering and Physical Sciences, University of Surrey, Guildford, Surrey, UK
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Xinqi Chen
10, Evanston, Illinois, USA
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Matthew J. Collins
11The GLOBE Institute, Faculty of Health and Medical Sciences, University of Copenhagen, Copenhagen, Denmark
12McDonald Institute for Archaeological Research, University of Cambridge, UK
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Jorune Sakalauskaite
13Department of Life Sciences and Systems Biology, University of Turin, Turin, Italy
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Meaghan Mackie
11The GLOBE Institute, Faculty of Health and Medical Sciences, University of Copenhagen, Copenhagen, Denmark
14Novo Nordisk Foundation Center for Protein Research, University of Copenhagen, Copenhagen, Denmark
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Federica Dal Bello
15Department of Molecular Biotechnology and Health Sciences, University of Turin, Turin, Italy
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Marc R. Dickinson
4Department of Chemistry, University of York, York, UK
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Mark A. Stevenson
5School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne, UK
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Paul Donohoe
5School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne, UK
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Philipp R. Heck
1Integrative Research Center, Field Museum of Natural History, Chicago, Illinois, USA
16Robert A. Pritzker Center for Meteorics and Polar Studies, Field Museum of Natural History, Chicago, Illinois, USA
17Department of the Geophysical Sciences, University of Chicago, Chicago, Illinois, USA
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Beatrice Demarchi
13Department of Life Sciences and Systems Biology, University of Turin, Turin, Italy
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Kirsty E. H. Penkman
4Department of Chemistry, University of York, York, UK
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Abstract

Rates of peptide bond hydrolysis and other diagenetic reactions are not favourable for Mesozoic protein survival. Proteins hydrolyse into peptide fragments and free amino acids that, in open systems such as bone, can leach from the specimen and be further degraded. However, closed systems are more likely to retain degradation products derived from endogenous proteins. Amino acid racemisation data in experimental and subfossil material suggests that mollusc shell and avian eggshell calcite crystals can demonstrate closed system behaviour, retaining endogenous amino acids. Here, high-performance liquid chromatography reveals that the intra-crystalline fraction of Late Cretaceous (estimated ~80 Ma) titanosaur sauropod eggshell is enriched in some of the most stable amino acids (Glx, Gly, Ala, and possibly Val) and those that racemise are fully racemic, despite being some of the slowest racemising amino acids. These results are consistent with degradation trends deduced from modern, thermally matured, sub-fossil, and ~3.8 Ma avian eggshell, as well as ~30 Ma calcitic mollusc opercula. Selective preservation of certain fully racemic amino acids, which do not racemise in-chain, along with similar concentrations of free versus total hydrolysable amino acids, likely suggests complete hydrolysis of original peptides. Liquid chromatography-tandem mass spectrometry supports this hypothesis by failing to detect any non-contamination peptide sequences from the Mesozoic eggshell. Pyrolysis-gas chromatography-mass spectrometry reveals pyrolysates consistent with amino acids as well as aliphatic hydrocarbon homologues that are not present in modern eggshell, suggestive of kerogen formation deriving from eggshell lipids. Raman spectroscopy yields bands consistent with various organic molecules, possibly including N-bearing molecules or geopolymers. These closed-system amino acids are possibly the most thoroughly supported non-avian dinosaur endogenous protein-derived constituents, at least those that have not undergone oxidative condensation with other classes of biomolecules. Biocrystal matrices can help preserve mobile organic molecules by trapping them (perhaps with the assistance of resistant organic polymers), but trapped organics are nevertheless prone to diagenetic degradation even if such reactions might be slowed in exceptional circumstances. The evidence for complete hydrolysis and degradation of most amino acids in the eggshell raises concern about the validity of reported polypeptide sequences from open-system non-avian dinosaur bone and other Mesozoic fossils.

Competing Interest Statement

The authors have declared no competing interest.

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NON-AVIAN DINOSAUR EGGSHELL CALCITE CONTAINS ANCIENT, ENDOGENOUS AMINO ACIDS
Evan T. Saitta, Jakob Vinther, Molly K. Crisp, Geoffrey D. Abbott, Thomas G. Kaye, Michael Pittman, Ian Bull, Ian Fletcher, Xinqi Chen, Matthew J. Collins, Jorune Sakalauskaite, Meaghan Mackie, Federica Dal Bello, Marc R. Dickinson, Mark A. Stevenson, Paul Donohoe, Philipp R. Heck, Beatrice Demarchi, Kirsty E. H. Penkman
bioRxiv 2020.06.02.129999; doi: https://doi.org/10.1101/2020.06.02.129999
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NON-AVIAN DINOSAUR EGGSHELL CALCITE CONTAINS ANCIENT, ENDOGENOUS AMINO ACIDS
Evan T. Saitta, Jakob Vinther, Molly K. Crisp, Geoffrey D. Abbott, Thomas G. Kaye, Michael Pittman, Ian Bull, Ian Fletcher, Xinqi Chen, Matthew J. Collins, Jorune Sakalauskaite, Meaghan Mackie, Federica Dal Bello, Marc R. Dickinson, Mark A. Stevenson, Paul Donohoe, Philipp R. Heck, Beatrice Demarchi, Kirsty E. H. Penkman
bioRxiv 2020.06.02.129999; doi: https://doi.org/10.1101/2020.06.02.129999

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