Synchrotron x-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry
Abstract
A key feature of the pigment melanin is its high binding affinity for trace metal ions. In modern vertebrates trace metals associated with melanosomes, melanin-rich organelles, can show tissue-specific and taxon-specific distribution patterns. Such signals preserve in fossil melanosomes, informing on the anatomy and phylogenetic affinities of fossil vertebrates. Fossil and modern melanosomes, however, often differ in trace metal chemistry; in particular, melanosomes from fossil vertebrate eyes are depleted in Zn and enriched in Cu relative to their extant counterparts. Whether these chemical differences are biological or taphonomic in origin is unknown, limiting our ability to use melanosome trace metal chemistry to test palaeobiological hypotheses. Here, we use maturation experiments on eye melanosomes from extant vertebrates and synchrotron rapid scan-x-ray fluorescence analysis to show that thermal maturation can dramatically alter melanosome trace element chemistry. In particular, maturation of melanosomes in Cu-rich solutions results in significant depletion of Zn, probably due to low pH and competition effects with Cu. These results confirm fossil melanosome chemistry is susceptible to alteration due to variations in local chemical conditions during diagenesis. Maturation experiments can provide essential data on melanosome chemical taphonomy required for accurate interpretations of preserved chemical signatures in fossils.
- Authors:
-
- Univ. College Cork (United Kingdom)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1769619
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Palaeontology
- Additional Journal Information:
- Journal Volume: 64; Journal Issue: 1; Journal ID: ISSN 0031-0239
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 59 BASIC BIOLOGICAL SCIENCES; fossil; soft tissue; taphonomy; synchrotron x‐ray fluorescence
Citation Formats
Rogers, Christopher S., Webb, Samuel M., and McNamara, Maria E. Synchrotron x-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry. United States: N. p., 2020.
Web. doi:10.1111/pala.12506.
Rogers, Christopher S., Webb, Samuel M., & McNamara, Maria E. Synchrotron x-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry. United States. https://doi.org/10.1111/pala.12506
Rogers, Christopher S., Webb, Samuel M., and McNamara, Maria E. Tue .
"Synchrotron x-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry". United States. https://doi.org/10.1111/pala.12506. https://www.osti.gov/servlets/purl/1769619.
@article{osti_1769619,
title = {Synchrotron x-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry},
author = {Rogers, Christopher S. and Webb, Samuel M. and McNamara, Maria E.},
abstractNote = {A key feature of the pigment melanin is its high binding affinity for trace metal ions. In modern vertebrates trace metals associated with melanosomes, melanin-rich organelles, can show tissue-specific and taxon-specific distribution patterns. Such signals preserve in fossil melanosomes, informing on the anatomy and phylogenetic affinities of fossil vertebrates. Fossil and modern melanosomes, however, often differ in trace metal chemistry; in particular, melanosomes from fossil vertebrate eyes are depleted in Zn and enriched in Cu relative to their extant counterparts. Whether these chemical differences are biological or taphonomic in origin is unknown, limiting our ability to use melanosome trace metal chemistry to test palaeobiological hypotheses. Here, we use maturation experiments on eye melanosomes from extant vertebrates and synchrotron rapid scan-x-ray fluorescence analysis to show that thermal maturation can dramatically alter melanosome trace element chemistry. In particular, maturation of melanosomes in Cu-rich solutions results in significant depletion of Zn, probably due to low pH and competition effects with Cu. These results confirm fossil melanosome chemistry is susceptible to alteration due to variations in local chemical conditions during diagenesis. Maturation experiments can provide essential data on melanosome chemical taphonomy required for accurate interpretations of preserved chemical signatures in fossils.},
doi = {10.1111/pala.12506},
journal = {Palaeontology},
number = 1,
volume = 64,
place = {United States},
year = {Tue Oct 20 00:00:00 EDT 2020},
month = {Tue Oct 20 00:00:00 EDT 2020}
}
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Works referenced in this record:
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
Fossilization of Soft Tissue in the Laboratory
journal, March 1993
- Briggs, D. E. G.; Kear, A. J.
- Science, Vol. 259, Issue 5100
Binding of Metal Ions to Melanin and Their Effects on the Aerobic Reactivity¶
journal, January 2004
- Hong, Lian; Liu, Yan; Simon, John D.
- Photochemistry and Photobiology, Vol. 80, Issue 3
Tissue-specific geometry and chemistry of modern and fossilized melanosomes reveal internal anatomy of extinct vertebrates
journal, August 2019
- Rossi, Valentina; McNamara, Maria E.; Webb, Sam M.
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 36
Molecular preservation of the pigment melanin in fossil melanosomes
journal, January 2012
- Lindgren, Johan; Uvdal, Per; Sjövall, Peter
- Nature Communications, Vol. 3, Issue 1
High-performance liquid chromatography estimation of cross-linking of dihydroxyindole moiety in eumelanin
journal, March 2013
- Ito, Shosuke; Wakamatsu, Kazumasa; Glass, Keely
- Analytical Biochemistry, Vol. 434, Issue 2
Insight into the Binding of Divalent Cations to Sepia Eumelanin from IR Absorption Spectroscopy
journal, January 2006
- Hong, Lian; Simon, John D.
- Photochemistry and Photobiology, Vol. 82, Issue 5
Ion-Exchange and Adsorption of Fe(III) by Sepia Melanin
journal, June 2004
- Liu, Yan; Hong, Lian; Kempf, Valerie R.
- Pigment Cell Research, Vol. 17, Issue 3
Experimental maturation of feathers: implications for reconstructions of fossil feather colour
journal, June 2013
- McNamara, Maria E.; Briggs, Derek E. G.; Orr, Patrick J.
- Biology Letters, Vol. 9, Issue 3
Analyses of Soft Tissue from Tyrannosaurus rex Suggest the Presence of Protein
journal, April 2007
- Schweitzer, M. H.; Suo, Z.; Avci, R.
- Science, Vol. 316, Issue 5822
The MicroAnalysis Toolkit: X-ray Fluorescence Image Processing Software
conference, January 2011
- Webb, S. M.; McNulty, Ian; Eyberger, Catherine
- THE 10TH INTERNATIONAL CONFERENCE ON X-RAY MICROSCOPY, AIP Conference Proceedings
Chemical, experimental, and morphological evidence for diagenetically altered melanin in exceptionally preserved fossils
journal, September 2015
- Colleary, Caitlin; Dolocan, Andrei; Gardner, James
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 41
Alternative origin of aliphatic polymer in kerogen
journal, January 2000
- Stankiewicz, B. A.; Briggs, D. E. G.; Michels, R.
- Geology, Vol. 28, Issue 6
Protein Sequences from Mastodon and Tyrannosaurus Rex Revealed by Mass Spectrometry
journal, April 2007
- Asara, J. M.; Schweitzer, M. H.; Freimark, L. M.
- Science, Vol. 316, Issue 5822
Data from: Synchrotron-X-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry
dataset, January 2019
- Rogers, Christopher
- Dryad
Expansion for the Brachylophosaurus canadensis Collagen I Sequence and Additional Evidence of the Preservation of Cretaceous Protein
journal, January 2017
- Schroeter, Elena R.; DeHart, Caroline J.; Cleland, Timothy P.
- Journal of Proteome Research, Vol. 16, Issue 2
Binding of Metal Ions to Melanin and Their Effects on the Aerobic Reactivity¶
journal, November 2004
- Hong, Lian; Liu, Yan; Simon, John D.
- Photochemistry and Photobiology, Vol. 80, Issue 3
Melanogenesis and associated cytotoxic reactions: Applications to insect innate immunity
journal, May 2005
- Nappi, A. J.; Christensen, B. M.
- Insect Biochemistry and Molecular Biology, Vol. 35, Issue 5
Melano-macrophage centres and their role in fish pathology
journal, September 2003
- Agius, C.; Roberts, R. J.
- Journal of Fish Diseases, Vol. 26, Issue 9
Molecular analyses of dinosaur osteocytes support the presence of endogenous molecules
journal, January 2013
- Schweitzer, Mary Higby; Zheng, Wenxia; Cleland, Timothy P.
- Bone, Vol. 52, Issue 1
Current Understanding of the Binding Sites, Capacity, Affinity, and Biological Significance of Metals in Melanin
journal, July 2007
- Hong, Lian; Simon, John D.
- The Journal of Physical Chemistry B, Vol. 111, Issue 28
Comparison of Structural and Chemical Properties of Black and Red Human Hair Melanosomes¶
journal, January 2005
- Liu, Yan; Hong, Lian; Wakamatsu, Kazumasa
- Photochemistry and Photobiology, Vol. 81, Issue 1
Pheomelanin pigment remnants mapped in fossils of an extinct mammal
journal, May 2019
- Manning, Phillip L.; Edwards, Nicholas P.; Bergmann, Uwe
- Nature Communications, Vol. 10, Issue 1
Hierarchical biota-level and taxonomic controls on the chemistry of fossil melanosomes revealed using synchrotron X-ray fluorescence
journal, June 2020
- Rossi, Valentina; Webb, Samuel M.; McNamara, Maria E.
- Scientific Reports, Vol. 10, Issue 1
Adsorption of Pb(II) and Cd(II) by Squid Ommastrephes bartrami Melanin
journal, January 2009
- Chen, Shiguo; Xue, Changhu; Wang, Jingfeng
- Bioinorganic Chemistry and Applications, Vol. 2009
Trace Metals as Biomarkers for Eumelanin Pigment in the Fossil Record
journal, June 2011
- Wogelius, R. A.; Manning, P. L.; Barden, H. E.
- Science, Vol. 333, Issue 6049
Présence du genre Lepidocottus Sauvage, 1875 (Teleostei, Gobioidei) dans l'Oligocène inférieur des environs de Céreste (Alpes-de-Haute-Provence, France)
journal, June 2015
- Gaudant, Jean
- Geodiversitas, Vol. 37, Issue 2
Evidence of proteins, chromosomes and chemical markers of DNA in exceptionally preserved dinosaur cartilage
journal, January 2020
- Bailleul, Alida M.; Zheng, Wenxia; Horner, John R.
- National Science Review, Vol. 7, Issue 4
Fossilization of melanosomes via sulfurization
journal, April 2016
- McNamara, Maria E.; van Dongen, Bart E.; Lockyer, Nick P.
- Palaeontology, Vol. 59, Issue 3
How Complexity Originates: The Evolution of Animal Eyes
journal, December 2015
- Oakley, Todd H.; Speiser, Daniel I.
- Annual Review of Ecology, Evolution, and Systematics, Vol. 46, Issue 1
The Protective Role of Melanin Against UV Damage in Human Skin†
journal, November 2007
- Brenner, Michaela; Hearing, Vincent J.
- Photochemistry and Photobiology, Vol. 84, Issue 3
Synchrotron X-ray absorption spectroscopy of melanosomes in vertebrates and cephalopods: implications for the affinity of Tullimonstrum
journal, October 2019
- Rogers, Christopher S.; Astrop, Timothy I.; Webb, Samuel M.
- Proceedings of the Royal Society B: Biological Sciences, Vol. 286, Issue 1913
The calcareous concretions (cementsten) in the Fur Formation
(Paleogene, Denmark): isotopic evidence of early diagenetic
growth
journal, July 1996
- Pedersen, Gunver Krarup; Buchardt, Bjørn
- Bulletin of the Geological Society of Denmark, Vol. 43
Data from: Synchrotron-X-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry
dataset, January 2019
- Rogers, Christopher
- Dryad
Works referencing / citing this record:
Data from: Synchrotron-X-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry
dataset, January 2019
- Rogers, Christopher
- Dryad
Data from: Synchrotron-X-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry
dataset, January 2019
- Rogers, Christopher
- Dryad