Leaf metallome preserved over 50 million years

Edwards, Nicholas P.; Manning, Phillip L.; Bergmann, Uwe; Larson, Peter L.; Dongen, Bart E. van; Sellers, William I.; Webb, Samuel M.; Sokaras, Dimosthenis; Alonso‐Mori, R.; Ignatyev, Konstantin; Barden, Holly E.; Veelen, Arjen van; Anné, Jennifer; Egerton, Victoria M.; Wogelius, R. A.

doi:10.1039/c3mt00242j

Cited by 36 publications

(50 citation statements)

References 34 publications

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“…To obtain rapid scanning, a full energy-dispersive X-ray spectrum is not recorded for each pixel [20]. The element windows are selected by collecting a raw energy-dispersive X-ray spectrum from 10 to 20 raster lines over an area of the map containing the majority of the different materials present in the sample (e.g.…”

Section: Methodsmentioning

confidence: 99%

“…However, the distribution and dilute concentrations of key trace elements that are crucial to maintaining healthy bone are difficult to map within discrete biological structures. The advent of synchrotron-based imaging of biological and palaeontological samples is helping address these issues [17–20]. …”

Section: Introductionmentioning

confidence: 99%

“…SRS–XRF has been optimized to allow multi-element mapping and can also be combined with X-ray absorption spectroscopy (XAS) [17–20,39,40]. This allows for the determination of the atomic coordination of a particular element (how it is bound to other elements).…”

Section: Introductionmentioning

confidence: 99%

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Synchrotron imaging reveals bone healing and remodelling strategies in extinct and extant vertebrates

Anné

Edwards

Wogelius

et al. 2014

J. R. Soc. Interface.

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Current understanding of bone healing and remodelling strategies in vertebrates has traditionally relied on morphological observations through the histological analysis of thin sections. However, chemical analysis may also be used in such interpretations, as different elements are known to be absorbed and used by bone for different physiological purposes such as growth and healing. These chemical signatures are beyond the detection limit of most laboratory-based analytical techniques (e.g. scanning electron microscopy). However, synchrotron rapid scanning–X-ray fluorescence (SRS–XRF) is an elemental mapping technique that uniquely combines high sensitivity (ppm), excellent sample resolution (20–100 µm) and the ability to scan large specimens (decimetre scale) approximately 3000 times faster than other mapping techniques. Here, we use SRS–XRF combined with microfocus elemental mapping (2–20 µm) to determine the distribution and concentration of trace elements within pathological and normal bone of both extant and extinct archosaurs (Cathartes aura and Allosaurus fragilis). Results reveal discrete chemical inventories within different bone tissue types and preservation modes. Chemical inventories also revealed detail of histological features not observable in thin section, including fine structures within the interface between pathological and normal bone as well as woven texture within pathological tissue.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synchrotron imaging reveals bone healing and remodelling strategies in extinct and extant vertebrates

Anné

Edwards

Wogelius

et al. 2014

J. R. Soc. Interface.

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“…; Edwards et al . ). Points of interest can be selected by using a microscope, set at the beamline to indicate the exact position where the beam hit the sample.…”

Section: Yttrium Mappingmentioning

confidence: 97%

Show me your yttrium, and I will tell you who you are: implications for fossil imaging

2018

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The development of X‐ray tomography in the last decade has led to a revolution in palaeontology by providing a means of imaging 3D fossils. In turn, imaging of flat fossils has strongly benefitted from critical improvement of synchrotron X‐ray fluorescence (XRF). The latter, which allows the mapping of 2D distributions of major‐to‐trace elements over decimetre‐scale objects, usually targets metals with atomic number (Z) up to strontium (K‐shell emission lines); in the same energy domain, L‐shell emission lines of heavier elements (particularly lead) can also be analysed. A fluorescence signal from strontium can escape from a depth of a few 100 μm in fossils, thereby revealing, due to its substitution for calcium in calcium phosphates (apatite group minerals and bone), hidden fossil bone or phosphatized remains. Nonetheless, strontium similarly substitutes for calcium in calcium carbonates, resulting in the absence of contrast when fossils are preserved in limestone. Here, we show that this issue can easily be overcome by using X‐rays slightly higher in energy (17.2 keV and above) to excite and detect yttrium fluorescence. Together with lanthanides (collectively known as the rare earth elements), yttrium preferentially substitutes for calcium in calcium phosphates, offering anatomical contrasts for a wider range of fossils. This is demonstrated here for three fossils (vertebrate and invertebrate) from different ages and depositional environments. We then discuss the different chemical behaviours of strontium and yttrium in calcium phosphates and carbonates. Although yttrium is also found in other (rarer) minerals, its mapping using synchrotron XRF could be used as a proxy to pinpoint calcium phosphates in fossils and other geological materials.

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“…Spectra were fit using PyMCA software from fundamental parameters (Solé et al 2007). Further details of methods are published in Bergmann et al (2012), Anné et al (2014) and Edwards et al (2014).…”

Section: Synchrotron Rapid Scanning X-ray Fluorescence (Srs-xrf)mentioning

confidence: 99%

Bacteria or melanosomes? A geochemical analysis of micro-bodies on a tadpole from the Oligocene Enspel Formation of Germany

Barden

Bergmann

Edwards

et al. 2014

Palaeobio Palaeoenv

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Many exceptionally preserved fossils have long been thought the product of preservation by bacterial autolithification, based largely upon the presence of, micronsized, spherical or elongate bodies on their surface. This has recently been challenged by studies of similar fossils which cite morphological and geochemical evidence that these structures could be fossilized melanosomes, melanin-containing organelles. We geochemically analysed a tadpole from the Oligocene Enspel Formation, Germany, which displays such spherical bodies on its surface. Pyrolysis gas chromatography mass spectroscopy (Py-GCMS) and Fourier transform infrared spectrometry (FTIR) indicate that the organic remains of the tadpole are original and are not the result of external contamination, shown by the different chemical compositions of the fossil and its enclosing matrix. Py-GCMS also demonstrates the presence of bacterial and plant biomarkers in the matrix but not the tadpole, suggesting that the spherical bodies are unlikely to be bacterial, and also that such fossils do not develop their dark colour from incorporating plant material, as has been suggested. X-ray absorption spectroscopy (XAS) shows high levels of organically bound Zn(II) in the fossilized soft tissue, a metal known to chelate both eu-and pheomelanin.The zinc in the tadpole shows greater similarity to that bound in pheomelanized extant samples than to that in eumelanized ones. Though further geochemical analysis of both pure pheomelanin and bacterial samples is required to completely exclude a bacterial origin, these results are in line with a pheomelanic origin for the spherical bodies on the tadpole.

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Leaf metallome preserved over 50 million years

Cited by 36 publications

References 34 publications

Synchrotron imaging reveals bone healing and remodelling strategies in extinct and extant vertebrates

Synchrotron imaging reveals bone healing and remodelling strategies in extinct and extant vertebrates

Show me your yttrium, and I will tell you who you are: implications for fossil imaging

Bacteria or melanosomes? A geochemical analysis of micro-bodies on a tadpole from the Oligocene Enspel Formation of Germany

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