Abstract
Biophotonic nanostructures rarely withstand fossilization processes occurring after burial over geologic time. Even more distinctive is a change introduced to the optical properties during diagenetic processes resulting in a different optical appearance. Here, we report and explain the optical appearance of centric diatom frustules obtained from ash-bearing carbonate-cemented concretions on the Greifswalder Oie island (Pomeranian Bay, Germany, southern Baltic Sea). The ultrastructural and mineralogical analysis of the fossil frustules were carried out using electron microscopy techniques and were correlated to the macroscopic and microscopic optical appearance of the frustules before and after acid etching. The unique optical properties of the fossil diatoms were associated with diagenetic nanocrystalline calcite filling the frustules’ areolae. This fill created the macroscopic pale-yellow colour of many frustules, a microscopic iridescence probably associated with diffraction grating behaviour, and microscopic colour rings. The results highlight the unique permineralization process of diatom frustules and might be an addition to the emerging studies on frustule optics and photonics.
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References
Ansorge J (1997) Insekten aus einem untereozänen Zementsteingeschiebe von Lubmin (Vorpommern). Arch Geschiebekde 2:261–264
Ansorge J (2000) Insekten aus Zementsteinen (Moler) vom Typ Greifswalder Oie. Geschiebekde Aktuell 16:43–45
Barrows FP, Bartl MH (2014) Photonic structures in biology: a possible blueprint for nanotechnology. Nanomater Nanotechnol 4:1. https://doi.org/10.5772/58289
Barthlott W, Neinhuis C (1997) Purity of the sacred lotus, or escape from contamination in biological surfaces. Planta 202:1–8. https://doi.org/10.1007/s004250050096
Berggren WA, Kent DV, Swisher CC, Aubry M-P (1995) A revised Cenozoic geochronology and chronostratigraphy. In: Berggren WA, Kent DV, Aubry M-P (eds) Geochronology, time scales and global stratigraphic correlation. Society for Sedimentary Geology, Tulsa, pp 129–212. https://doi.org/10.2110/pec.95.04.0129
Bettenstaedt F, Fahrion H, Hiltermann H, Wick W (1962) Tertiär Norddeutschlands. Leitfossilien der Mikropaläontologie. Arbeitskreis deutscher Mikropaläontologen, Berlin, pp 339–378
Bidgood MD, Mitlehner AG, Jones GD, Jutson DJ (1999) Towards a stable and agreed nomenclature for North Sea Tertiary diatom floras – the `Coscinodiscus` problem. In: Jones RW, Simmons MD (eds) Biostratigraphy in Production and Development Geology. Geological Society, Special Publications 152. Geological Society, London, pp 139–153. https://doi.org/10.1144/GSL.SP.1999.152.01.08
Böhmecke E (1998) Fossile Diatomeen in Edelopalerhaltung. Fundgrube 34:102–108
Cai C, Tihelka E, Pan Y, Yin Z, Jiang R, Xia F, Huang D (2020) Structural colours in diverse Mesozoic insects. Proc Royal Soc B Biol 287:20200301. https://doi.org/10.1098/rspb.2020.0301
Chambers LM, Pringle M, Fitton JG, Larsen LM, Perdersen AK, Parrish R (2003). Recalibration of the Palaeocene-Eocene boundary (P-E) using high precision U-Pb and Ar-Ar isotopic dating. Geophysical Research Abstracts, EGS-AGU-EUG Joint Assembly, Nice, 6th-11th April 2003, 5:9681–9682
Chen F, Huang Y, Li R, Zhang S, Wang B, Zhang W, Wu X, Jiang Q, Wang F, Zhang R (2021) Bio-inspired structural colors and their applications. Chem Comm 57:13448–13464. https://doi.org/10.1039/d1cc04386b
Crawford SA, Higgins MJ, Mulvaney P, Wetherbee R (2001) Nanostructure of the diatom frustule as revealed by Atomic Force and scanning electron microscopy. J Phycol 37:543–554. https://doi.org/10.1046/j.1529-8817.2001.037004543.x
De Tommasi E (2016) Light manipulation by single cells: The case of diatoms. J Spectrosc 2016:1–13. https://doi.org/10.1155/2016/2490128
De Stefano L, Rotiroti L, De Stefano M, Lamberti A, Lettieri S, Setaro A, Maddalena P (2009) Marine diatoms as optical biosensors. Biosens Bioelectron 24:1580–1584. https://doi.org/10.1016/j.bios.2008.08.016
Deecke W (1903) Neue Materialien zur Geologie von Pommern (Teil 2). Mitt Naturwiss Ver Neuvorpommern u Rügen 34:1–55
Dumanli AG, Savin T (2016) Recent advances in the biomimicry of structural colours. Chem Soc Rev 45:6698–6724
Eetvelde Yv, Cornet C (2002) Some Eocene species of marine pyritized diatoms in the core of Saint-Josse (France). Diatom Res 17:423–435. https://doi.org/10.1080/0269249X.2002.9705559
Eetvelde Yv, Dupuis C, Cornet C (2004) Pyritized diatoms: a good fossil marker in the Upper Paleocene-Lower Eocene sediments from the Belgian and Dieppe-Hampshire Basins. Neth J Geosci 83:173–178
Elbert J, Klose H (1904) Kreide und Paleocän auf der Greifswalder Oie. Jahresber Geogr Ges Greifswald 8:111–139
Fuhrmann T, Landwehr S, El Rharbi-Kucki M, Sumper M (2004) Diatoms as living photonic crystals. Appl Phys B Lasers O 78:257–260. https://doi.org/10.1007/s00340-004-1419-4
Gagel C (1907) Über das Alter und die Lagerungsverhältnisse des Schwarzenbecker Tertiärs. Jb Kgl Preuss Geol Landesanst Bergakad Berlin 27:399–417
Gagel C (1910) Über die untereozänen Tuffschichten und die paleozänen Transgressionen in Norddeutschland. Jb Kgl Preuss Geol Landesanst Bergakad Berlin 28:150–168
Geyssant J (2001) Features and characteristics of calcium carbonate. In: Tegethoff FW (ed) calcium carbonate. Birkhäuser, Basel, pp 2–15. https://doi.org/10.1007/978-3-0348-8245-3_1
Ghobara MM, Mousa AM (2019) Diatomite in use: nature, modification, commercial applications, and prospective trends. Diatoms: fundamentals and applications. Wiley-Scrivener, Beverly, pp 471–510. https://doi.org/10.1002/9781119370741.ch19
Ghobara MM, Mazumder N, Vinayak V, Reissig L, Gebeshuber IC, Tiffany MA, Gordon R (2019) On light and diatoms: a photonics and photobiology review. In: Seckbach J, Gordon R (eds) Diatoms: fundamentals and applications. Wiley-Scrivener, Beverly, pp 471–510. https://doi.org/10.1002/9781119370741.ch7
Goessling JW, Frankenbach S, Ribeiro L, Serôdio J, Kühl M (2018) Modulation of the light field by valve optical properties of raphid diatoms: Implications for niche differentiation in the microphytobenthos. Mar Ecol Prog Ser 588:29–42. https://doi.org/10.3354/meps12456
Goessling JW, Wardley WP, Lopez-Garcia M (2020) Highly reproducible, bio-based slab photonic crystals grown by diatoms. Adv Sci 7:1903726. https://doi.org/10.1002/advs.201903726
Gordon R, Losic D, Tiffany MA, Nagy SS, Sterrenburg FA (2009) The glass menagerie: diatoms for novel applications in nanotechnology. Trends Biotechnol 27:116–127. https://doi.org/10.1016/j.tibtech.2008.11.003
Grönwall KA (1903) Løse Blokke fra Nordtyskland af Stenarter, der indeholde vulkansk Aske. Medd Dansk Geol Foren 9:13–20
Henrici H, Hiltermann H (1962) London-Ton und Moler-Formation und andere Ablagerungen der Tertiär-Meere bei Lamstedt (NW von Stadel). Ber Naturhist Ges Hannover 106:27–39
Hinz-Schallreuter I, Schallreuter R (2000) Geschiebestudien auf der Greifswalder Oie. 1. Oiella voigti aus einem Zementstein (Paläogen). Geschiebekde Aktuell 16:117–126
Hu D, Clarke JA, Eliason CM, Qiu R, Li Q, Shawkey MD, Zhao C, DAlba L, Jiang J, Xu X (2018) A bony-crested Jurassic dinosaur with evidence of iridescent plumage highlights complexity in early paravian evolution. Nat Commun 9:1–12. https://doi.org/10.1038/s41467-017-02515-y
Illies H (1949) Die Lithogenese des Untereozäns in Nordwestdeutschland. Mitt Geol Staatsinst 18:7–44
Jeffryes C, Gutu T, Jiao J, Rorrer GL (2008) Peptide-mediated deposition of nanostructured TiO2 into the periodic structure of Diatom Biosilica. J Mater Res 23:3255–3262. https://doi.org/10.1557/jmr.2008.0402
Jeffryes C, Campbell J, Li H, Jiao J, Rorrer G (2011) The potential of diatom nanobiotechnology for applications in solar cells, batteries, and electroluminescent devices. Energy Environ Sci 4:3930–3941. https://doi.org/10.1039/C0EE00306A
Kieu K, Li C, Fang Y, Cohoon G, Herrera OD, Hildebrand M, Sandhage KH, Norwood RA (2014) Structure-based optical filtering by the silica microshell of the centric marine diatom Coscinodiscus wailesii. Opt Express 22:15992–15999. https://doi.org/10.1364/OE.22.015992
Kinoshita S, Yoshioka S, Miyazaki J (2008) Physics of structural colors. Rep Prog Phys 71:076401. https://doi.org/10.1088/0034-4885/71/7/076401
Knaust D (1992) Ein Molervorkommen (Paläogen) auf der Greifswalder Oie (Ostsee). Arch Geschiebekde 1:291–304
Knaust D (1995) Die geologische Entwicklung der Ostseeinsel Greifswalder Oie. Terra Nostra 95:47–96
Knecht M, Walsh T (2014) Bio-inspired nanotechnology. Springer, New York
Kwak JS, Kim TW (2010) A review of adhesion and friction models for gecko feet. Int J Precis Eng Manuf 11:171–186. https://doi.org/10.1007/s12541-010-0020-5
Larsen LM, Fitton JG, Pedersen AK (2003) Paleogene volcanic ash layers in the Danish Basin: compositions and source areas in the North Atlantic Igneous Province. Lithos 71:47–80. https://doi.org/10.1016/j.lithos.2003.07.001
Lierl H-J, Mende R (1991) Edelopal-Kieselalgen aus dem Moler Dänemarks. Geschiebekde Aktuell 7:159–163
Liesegang M, Milke R, Kranz C, Neusser G (2017) Silica nanoparticle aggregation in calcite replacement reactions. Sci Rep 7:1–6. https://doi.org/10.1038/s41598-017-06458-8
Losic D, Mitchell JG, Voelcker NH (2009) Diatomaceous lessons in nanotechnology and advanced materials. Adv Mater 21:2947–2958. https://doi.org/10.1002/adma.200803778
McCoy DE, McCoy VE, Mandsberg NK, Shneidman AV, Aizenberg J, Prum RO, Haig D (2019) Structurally assisted super black in colourful peacock spiders. Proc Roy Soc B Biol 286:20190589. https://doi.org/10.1098/rspb.2019.0589
McNamara ME, Briggs DEG, Orr PJ (2012) The controls on the preservation of structural color in fossil insects. Palaios 27:443–454. https://doi.org/10.2110/palo.2012.p12-027r
Obst K, Ansorge J (2010) Die Greifswalder Oie – ein einzigartiges Vorkommen von präpleistozänen Schollen und Geschieben in einer hoch deformierten quartären Abfolge. In: Lampe R, Lorenz S (eds) Eiszeitlandschaften in Mecklenburg-Vorpommern. Geozon Science Media, Greifswald, pp 132–158
Obst K, Ansorge J, Matting S, Hüneke H (2015) Early Eocene volcanic ashes on Greifswalder Oie and their depositional environment, with an overview of coeval ash-bearing deposits in northern Germany and Denmark. Int J Earth Sci 104:2179–2212. https://doi.org/10.1007/s00531-015-1203-1
Palmer CA (2020) Diffraction grating handbook. MKS instruments. Rochester
Parker AR, Townley HE (2007) Biomimetics of photonic nanostructures. Nat Nanotech 2:347–353. https://doi.org/10.1038/nnano.2007.152
Pedersen GK, Surlyk F (1983) The Fur Formation, a late Paleocene ash-bearing diatomite from northern Denmark. Bull Geol Soc Denmark 32:43–65
Reich M (2000) Diatomeen aus dem Moler (Paläogen) der Greifswalder Oie (Ostsee). Geschiebekde Aktuell 16:107–115
Round FE, Crawford RM, Mann DG (1990) Diatoms: biology and morphology of the genera. Cambridge University Press, Cambridge
Schulz P (1927) Diatomeen aus den norddeutschen Basalttuffen und -tuffgeschieben. Z Geschiebeforsch 3:66–78
Smol JP, Stoermer EF (2010) The diatoms: applications for the environmental and earth sciences. Cambridge University Press, Cambridge
Staesche K, Hiltermann H (1940) Mikrofaunen aus dem Tertiär Nordwestdeutschlands. Abh Reichsamts Bodenforsch Ger 201:1–23
Starkey T, Vukusic P (2013) Light manipulation principles in biological photonic systems. Nanophotonics 2:289–307. https://doi.org/10.1515/nanoph-2013-0015
Stavenga DG (2014) Thin film and multilayer optics cause structural colors of many insects and birds. Mater Today Proc 1:109–121. https://doi.org/10.1016/j.matpr.2014.09.007
Sumper M, Kröger N (2004) Silica formation in diatoms: the function of long-chain polyamines and Silaffins. J Mater Chem 14:2059–2065. https://doi.org/10.1039/b401028k
Sun J, Bhushan B, Tong J (2013) Structural coloration in nature. RSC Adv 3:14862–14889. https://doi.org/10.1039/C3RA41096J
Tröger WE (2017) Optische Bestimmung der gesteinsbildenden Minerale Teil I. In: Bambauer HU, Taborszky F, Trochim HD (eds) Bestimmungstabellen. Schweizerbart Science Publishers, Stuttgart
van den Akker TJHA, Kaminski MA, Gradstein FM, Wood J (2000) Campanian to Palaeocene biostratigraphy and palaeoenvironments in the Foula sub-basin, west of the Shetland Islands. J Micropalaeontol 19:23–43. https://doi.org/10.1144/jm.19.1.23
Wirth R (2004) Focused Ion Beam (FIB): a novel technology for advanced application of micro- and nanoanalysis in geosciences and applied mineralogy. Eur J Mineral 16:863–876. https://doi.org/10.1127/0935-1221/2004/0016-0863
Zhao Y, Xie Z, Gu H, Zhu C, Gu Z (2012) Bio-inspired variable structural color materials. Chem Soc Rev 41:3297. https://doi.org/10.1039/c2cs15267c
Acknowledgements
We sincerely thank the Editor-in-Chief Maurice Tucker, Mike Reich and an anonymous reviewer for their detailed comments. We would like to particularly acknowledge Ralf Milke (FU Berlin), who contributed to an earlier version of the manuscript but passed away in 2022. Jan Evers provided access to the SEM at the Institut für Geologische Wissenschaften of the Freie Universität Berlin, Germany. We thank Manfred Ruppel (Goethe Universität Frankfurt am Main, Germany) for collecting the SEM image 3b. Anja Schreiber (GFZ Potsdam, Germany) is thanked for FIB sample preparation.
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ML, MG, and SM were responsible for the project design. SM collected the samples. ML carried out the SEM analyses and light microscopy. TEM analyses were done by RW. The authors, except RM, discussed the results and submitted manuscript, which was written by ML, MG and SM.
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Liesegang, M., Ghobara, M., Matting, S. et al. The colourful optical appearance of centric diatom fossil frustules with diagenetic nanocrystalline calcite fill. Facies 70, 1 (2024). https://doi.org/10.1007/s10347-023-00675-6
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DOI: https://doi.org/10.1007/s10347-023-00675-6