Fossil shell of Pithocerithium rubiginosum (height is 1.5 cm) from the Miocene sediments of Nexing in Austria (left) and isolated reddish polyene pigments on calcium fluoride disc (diameter of disc is 2 cm) (right).
Photo: Klaus Wolkenstein
Another terrible week for creationists is continuing today with news that a team of researchers from the University of Göttingen and the Natural History Museum Vienna (NHMW) have shown that the red pigment frequently found associated with the shells of fossilised snails from the Middle Miocene is the pigment that would have been present in the living shells, and not, as had been suggested, the product of later reactions.
This makes these pigments, from the chemical group of polyenes which includes the carotenes that give the colour to the plumage of some birds and to carrots, the oldest known pigments ever discovered. The fossil snails, Pithocerithium rubiginosum, so named from the 'rusty red' pigment they often contain, are from the Middle Miocene deposits in the geologically important Vienna Basin:
What information do you have on the formation of the Vienna Basin? The Vienna Basin, also known as the Vienna Basin or Vienna Basin, is a geological formation located in Central Europe, primarily in Austria and Slovakia. It is a sedimentary basin that formed over millions of years through complex geological processes. Here's a brief overview of its formation:The University of Göttingen team have published their findings, open access, in the journal of the Palaeontological Association, Palaeontology and explain it in a University of Göttingen news release:Overall, the formation of the Vienna Basin is the result of a complex interplay of tectonic, sedimentary, and volcanic processes over millions of years. Today, it is an important geological and geographical feature of Central Europe, known for its rich sedimentary deposits and diverse landscapes.
- Tectonic Activity: The formation of the Vienna Basin is closely tied to the tectonic activity of the region. It is situated within the broader framework of the Pannonian Basin System, which includes several smaller basins in Central Europe. The basin's formation began during the Paleogene period (about 66 to 23 million years ago) as a result of the convergence of tectonic plates.
- Extensional Tectonics: During the Middle Miocene epoch (approximately 15 to 12 million years ago), extensional tectonic forces played a significant role in shaping the Vienna Basin. These forces caused the crust to stretch and thin, leading to the subsidence of the basin floor and the accumulation of sediments.
- Deposition: Sedimentation played a crucial role in filling the Vienna Basin. Rivers flowing from the surrounding mountain ranges, such as the Alps and the Carpathians, transported sediments into the basin. These sediments, including sand, clay, and gravel, gradually accumulated over time, forming thick layers of sedimentary rocks.
- Volcanic Activity: Volcanic activity also contributed to the formation of the Vienna Basin. During the Neogene period (about 23 to 2.6 million years ago), volcanic eruptions occurred in the region, depositing volcanic rocks and ash layers in the basin.
- Subsidence and Uplift: The Vienna Basin has experienced periods of subsidence and uplift throughout its geological history. Subsidence occurred as a result of the extensional tectonic forces, while uplift may have been caused by compressional tectonic forces or isostatic adjustments of the Earth's crust.
Presumably, the volcanic ash layers are key to dating the Middle Miocene deposits?
Yes, you're correct. Volcanic ash layers, also known as tephra, are indeed crucial for dating sedimentary deposits, including those from the Middle Miocene period in the Vienna Basin. Here's how they contribute to dating:In the case of the Vienna Basin, the presence of volcanic ash layers within Middle Miocene deposits provides valuable chronological markers that help researchers establish the timing of sedimentation events and understand the geological history of the basin more accurately.
- Absolute Dating: Volcanic ash layers often contain minerals, such as zircon, that can be dated using radiometric techniques like radiocarbon dating or potassium-argon dating. By determining the age of these volcanic ash layers, geologists can establish precise ages for the sedimentary deposits above and below them.
- Correlation: Volcanic ash layers can serve as marker beds, allowing geologists to correlate sedimentary sequences across different locations. If a particular ash layer is found in multiple sedimentary sections, it provides a reliable reference point for correlating the ages of those sections.
- Biostratigraphy: Volcanic ash layers can also be used in conjunction with fossil assemblages to refine the age estimates of sedimentary deposits. By comparing the fossils found within the ash layers to known fossil assemblages from other sites or periods, geologists can further constrain the age of the sediments.
Snail shells are often colourful and strikingly patterned. This is due to pigments that are produced in special cells of the snail and stored in the shell in varying concentrations. Fossil shells, on the other hand, are usually pale and inconspicuous because the pigments are very sensitive and have already decomposed. Residues of ancient colour patterns are therefore very rare. This makes this new discovery by researchers from the University of Göttingen and the Natural History Museum Vienna (NHMW) all the more astonishing: they found pigments in twelve-million-year-old fossilised snail shells. These are the world's first pigments from the chemical group of polyenes that have been preserved almost unchanged and found in fossils. The study was published in the journal Palaeontology.Technical details and background to the discovery are in the teams published paper:
Palaeontologists from the NHMW found snail shells of the superfamily Cerithioidea in Burgenland, Austria. The snails lived there twelve million years ago on the shores of a tropical sea. Professor Mathias Harzhauser at NHMW, who was involved in the discovery, explains: "It was unclear whether the patterns of reddish colour were from the original shell or were formed by later processes in the sediment." Researchers at Göttingen University’s Geoscience Center solved the mystery. They analysed the pigments using Raman spectroscopy. This involves irradiating samples with laser light. The scattered light reflected from the sample can be used to clearly identify chemical compounds. They detected pigments in the fossilised shells that belong to the polyene group of chemicals. These are organic compounds that include the well-known “carotenoids”, which are responsible for producing the vibrant red, orange and yellow colours seen in birds’ feathers, carrots and egg yolks, for instance.
Dr Klaus Wolkenstein, who led the study and has been researching the chemistry of fossil pigments at Göttingen University for many years, explains:Normally, after such a long period of time, the best we can hope for is that there are traces of degradation products of these chemicals. If degraded, however, these compounds would be devoid of colour. So, it was really surprising to discover these pigments, preserved almost intact, in fossils that are twelve million years old.
And so, another terrible month for creationists continues, or at least it would be if any of them had the courage to reverse out of their rabbit hole into the real world and look at some real-world evidence such as this. 12 million-year-old fossil snails, with ages verified by U-Pb dating of zircons in volcanic ash layers and from a formation in Eastern Europe that has been extensively explored and dated with multiple dating methods that all converge on a 12 million year age for the alluvial deposits, and that age meshes exactly with known tectonic activity that produced the formation.Abstract
Polyene pigments represent a major class of pigments in present-day organisms. Their occurrence in fossils has been frequently discussed, but to date no spectroscopic evidence has been found. Here, we use in situ Raman spectroscopy to examine the chemistry of exceptionally well-preserved gastropod shells with colour preservation from the Middle Miocene of the Vienna Basin (Austria, Hungary). Raman signals indicative of the presence of intact (i.e. non-hydrogenated) polyene pigments were obtained from fossil shells with reddish colour patterns, thus revealing the first record of intact polyenes in fossils. The observed Raman values are in good agreement with those of unmethylated (non-carotenoid) polyenes. Fossil polyene pigments were detected in representatives of the superfamily Cerithioidea, but not in representatives of other gastropod families with colour preservation found at the same localities, demonstrating that the occurrence of polyene pigments is taxon-specific. Our results show that Raman spectroscopy represents a valuable tool for the non-destructive screening of rare fossils with colour preservation for the occurrence of polyene pigments.
Polyene pigments are widely distributed in the three domains of life and are responsible for most yellow, orange and red colours observed in nature (Yabuzaki 2017; Maia et al. 2021). The dominant group among the polyene pigments are the carotenoids, but non-carotenoid polyenes such as the psittacofulvins have increasingly become the subject of recent research (Maia et al. 2021). The occurrence of polyene pigments in fossils has been discussed especially in the context of molluscan shell colour (Williams 2017.1; Wolkenstein 2022), plumage pigments (Thomas et al. 2014a, 2014.1b) and recent palaeocolour reconstructions (McNamara et al. 2016; Roy et al. 2020; Vinther 2020.1). However, because of the known susceptibility of polyenes to oxidation (Britton et al. 2008), the preservation potential of intact polyenes in sediments and fossils is generally considered to be low (Sinninghe Damsté & Koopmans 1997; Williams 2017.1), and to date no spectroscopic evidence for the preservation of intact polyene pigments in fossils has been reported.
Colour pattern preservation can be commonly found in Cenozoic molluscan shells (Hollingworth & Barker 1991). Many shell colour patterns that have faded to some extent have also been revealed using UV light (e.g. Krueger 1974; Dockery 1980; Caze et al.2010, 2011; Schneider et al. 2013; Hendricks 2015). By contrast, obvious colour preservation (i.e. preservation of distinct colours in fossils that goes beyond the usual brown tones) is rare. An outstanding example is the small gastropod Pithocerithium rubiginosum (Cerithiidae), representing one of the most abundant gastropod species of the Sarmatian (Middle Miocene) of the Central Paratethys (Harzhauser & Piller 2010.1). Many specimens of P. rubiginosum show a distinct red colouration of the beads of the spiral cords (Fig. 1A). This red colouration has been well known since the 19th century (Hörnes 1848) and it is so conspicuous that the species was named for it (from the Latin for ‘rusty red’) by Eichwald (1830, 1853). In addition to P. rubiginosum, colour preservation can be found in a number of other gastropods from the Vienna Basin. However, despite the often distinct colouration, until now no attempt has been made to chemically analyse the pigments of fossil gastropods.
FIG. 1
Examples of coloured Miocene and modern gastropods used for Raman measurements. A, Pithocerithium rubiginosum, Miocene, Nexing, Austria, NHMW 2023/0101/0001. B, Tiaracerithium pictum, Miocene, St Margarethen, Austria, NHMW 2023/0103/0001. C, Potamides disjunctus, Miocene, Fertőrákos, Hungary, NHMW 2023/0104/0002. D, Sarmatigibbula podolica, Miocene, Fertőrákos, Hungary, NHMW 2023/0104/0003. E, Megalotachea sylvestrina, Miocene, Nexing, Austria, NHMW 2023/0101/0003. F, Thericium vulgatum, modern, Mediterranean Sea, Malacological Collection of NHMW, NHMW 2023/0105/0001. Scale bar represents 1 cm.
A survey of the literature shows that even the pigments of present-day molluscs are merely known (Williams 2017.1). Some results concerning the pigments of present-day molluscs have been obtained using Raman analysis. Although Raman spectroscopy cannot be considered as a method for structure elucidation in the narrower sense, it provides valuable information on the molecular framework and the nature of bonding of unknown compounds. In situ Raman spectroscopy has suggested that polyene pigments are distributed in many present-day molluscs (Merlin & Delé-Dubois 1986; Barnard & de Waal 2006; Hedegaard et al. 2006.1; Ishikawa et al. 2019; Wade et al. 2019.1). Polyenes are polyunsaturated organic compounds that contain at least two conjugated carbon double bonds and include natural products such as isoprenoid carotenoids and unmethylated polyenes such as the psittacofulvins (Maia et al. 2021). Based on Raman data, those polyenes found in modern molluscs have generally been assigned as unmethylated polyenes (Merlin & Delé-Dubois 1986; Barnard & de Waal 2006; Hedegaard et al. 2006.1; Ishikawa et al. 2019).
In recent years, Raman spectroscopy has gained increasing popularity in the analysis of fossil samples, because it is a non-destructive method and measurements can be easily performed. On the other hand, some limitations and pitfalls have to be considered with the Raman analysis of fossil samples. In particular, the high autofluorescence of many fossils represents a serious problem, often making analysis impossible (Olcott Marshall & Marshall 2015.1; Geisler & Menneken 2021.2). In addition to inorganic compounds, Raman spectroscopy has been successfully applied to fossil organic materials such as amber (Winkler et al. 2001) and fossilized latex (Lönartz et al. 2023), although it should be considered that not all organic molecules are equally suitable for Raman analysis. A limitation for organic compounds is that especially in thermally more mature samples commonly only D and G bands of carbon are obtained (Peteya et al. 2017.2; Wolkenstein 2022). Moreover, in some recent Raman studies on fossil samples (e.g. Wiemann et al. 2018; McCoy et al. 2020.2) numerous quasi-periodic signals have been obtained over the full spectral range, which, however, are supposed to represent instrumental artefacts generated by interferences from intense background fluorescence at the edge filters (Alleon et al. 2021.2).
In order to explore the chemical nature of colourful fossil gastropod shells from the Vienna Basin as non-destructively as possible, we decided to investigate a set of representative specimens with Raman spectroscopy. This technique appears particularly suitable for the analysis of potential fossil polyene pigments, since polyenes are known to be strong Raman scatterers (signal enhancement by the resonance Raman effect) (e.g. Maia et al. 2021), thus allowing for the detection of even small amounts of pigment.
Ah! But the Middle Eastern authors of Genesis who hadn’t yet invented the wheel and described the Universe as a small flat place with a dome over it, that ran on magic, were incomparably more accurate than anything modern science can produce, or so a dwindling bunch of semi-literate and scientifically ignorant fools believe.
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