Protein sequences bound to mineral surfaces persist into deep time.
Proteins persist longer in the fossil record than DNA, but the longevity, survival mechanisms and substrates remain contested. Here, we demonstrate the role of mineral binding in preserving the protein sequence in ostrich (Struthionidae) eggshell, including from the palaeontological sites of Laetoli (3.8 Ma) and Olduvai Gorge (1.3 Ma) in Tanzania. By tracking protein diagenesis back in time we find consistent patterns of preservation, demonstrating authenticity of the surviving sequences. Molecular dynamics simulations of struthiocalcin-1 and -2, the dominant proteins within the eggshell, reveal that distinct domains bind to the mineral surface. It is the domain with the strongest calculated binding energy to the calcite surface that is selectively preserved. Thermal age calculations demonstrate that the Laetoli and Olduvai peptides are 50 times older than any previously authenticated sequence (equivalent to ~16 Ma at a constant 10°C).
BioArCh, Department of Archaeology, University of York, York, United Kingdom.
Beatrice
http://orcid.org/0000-0002-8398-4409
B
Demarchi
Department of Material Science and Engineering, University of Sheffield, Sheffield, United Kingdom.
Shaun
S
Hall
Department of Physics, University of York, York, United Kingdom.
Teresa
T
Roncal-Herrero
Department of Material Science and Engineering, University of Sheffield, Sheffield, United Kingdom.
Colin L
CL
Freeman
BioArCh, Department of Archaeology, University of York, York, United Kingdom.
Jos
J
Woolley
Department of Chemistry, University of York, York, United Kingdom.
Molly K
MK
Crisp
Department of Chemistry, University of York, York, United Kingdom.|Department of Mathematics, University of York, York, United Kingdom.
Julie
J
Wilson
Centre for GeoGenetics, Natural History Museum of Denmark, University of Copenhagen, Copenhagen, Denmark.
Anna
A
Fotakis
Advanced Proteomics Facility, Target Discovery Institute, Nuffield Department of Medicine, University of Oxford, Oxford, United Kingdom.
Roman
R
Fischer
Advanced Proteomics Facility, Target Discovery Institute, Nuffield Department of Medicine, University of Oxford, Oxford, United Kingdom.
Benedikt M
BM
Kessler
Novo Nordisk Foundation Center for Protein Research, Faculty of Health Sciences, University of Copenhagen, Copenhagen, Denmark.
Rosa
R
Rakownikow Jersie-Christensen
Novo Nordisk Foundation Center for Protein Research, Faculty of Health Sciences, University of Copenhagen, Copenhagen, Denmark.
Jesper V
JV
Olsen
Research Laboratory for Archaeology and the History of Art, University of Oxford, Oxford, United Kingdom.
James
J
Haile
Centre for GeoGenetics, Natural History Museum of Denmark, University of Copenhagen, Copenhagen, Denmark.|Molecular Ecology and Fisheries Genetics Laboratory, School of Biological Sciences, Bangor University, Bangor, United Kingdom.
Jessica
J
Thomas
Institute of Human Origins, SHESC, Arizona State University, Tempe, United States.|Centre for Coastal Palaeoscience, Nelson Mandela Metropolitan University, Port Elizabeth, South Africa.
Curtis W
CW
Marean
Department of Archaeology, University of Cape Town, Cape Town, South Africa.
John
J
Parkington
BioArCh, Department of Archaeology, University of York, York, United Kingdom.
Samantha
S
Presslee
Research Laboratory for Archaeology and the History of Art, University of Oxford, Oxford, United Kingdom.
Julia
J
Lee-Thorp
Research Laboratory for Archaeology and the History of Art, University of Oxford, Oxford, United Kingdom.
Peter
P
Ditchfield
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, United Kingdom.
Jacqueline F
JF
Hamilton
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, United Kingdom.
Martyn W
MW
Ward
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, United Kingdom.
Chunting Michelle
CM
Wang
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, United Kingdom.
Marvin D
MD
Shaw
Center for the Study of Human Origins, Department of Anthropology, New York University, New York, United States.
Terry
T
Harrison
Department of Prehistory, Complutense University of Madrid, Madrid, Spain.
Manuel
M
Domínguez-Rodrigo
Department of Mammalogy, American Museum of Natural History, New York, United States.
Ross DE
R
MacPhee
National Museum of Tanzania, Dar es Salaam, Tanzania.
Amandus
A
Kwekason
Research Laboratory for Archaeology and the History of Art, University of Oxford, Oxford, United Kingdom.
Michaela
http://orcid.org/0000-0001-9581-1882
M
Ecker
National Natural History Collections, Faculty of Life Sciences, The Hebrew University, Jerusalem, Israel.
Liora
L
Kolska Horwitz
Department of Anthropology, University of Toronto, Toronto, Canada.|Evolutionary Studies Institute, University of the Witwatersrand, Braamfontein, South Africa.
Michael
M
Chazan
Department of Physics, University of York, York, United Kingdom.
Roland
R
Kröger
Department of Chemistry, University of York, York, United Kingdom.|Centre of Excellence in Mass Spectrometry, University of York, New York, United States.
Jane
J
Thomas-Oates
Department of Material Science and Engineering, University of Sheffield, Sheffield, United Kingdom.
John H
JH
Harding
Centre for GeoGenetics, Natural History Museum of Denmark, University of Copenhagen, Copenhagen, Denmark.
Enrico
E
Cappellini
Department of Chemistry, University of York, York, United Kingdom.
Kirsty
K
Penkman
BioArCh, Department of Archaeology, University of York, York, United Kingdom.
Matthew J
MJ
Collins
Struthio camelus; biochemistry; biomineralization; eggshell; evolutionary biology; genomics; molecular dynamics; paleontology; paleoproteomics
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