I18-Microfocus Spectroscopy
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Phillip L.
Manning
,
Nicholas P.
Edwards
,
Uwe
Bergmann
,
Jennifer
Anne
,
William
Sellers
,
Arjen
Van Veelen
,
Dimosthenis
Sokaras
,
Victoria M.
Egerton
,
Roberto
Alonso-Mori
,
Konstantin
Ignatyev
,
Bart E.
Van Dongen
,
Kazumasa
Wakamatsu
,
Shosuke
Ito
,
Fabien
Knoll
,
Roy A.
Wogelius
Diamond Proposal Number(s):
[12948, 11865, 9488, 8597, 7749]
Open Access
Abstract: Recent progress has been made in paleontology with respect to resolving pigmentation in fossil material. Morphological identification of fossilized melanosomes has been one approach, while a second methodology using chemical imaging and spectroscopy has also provided critical information particularly concerning eumelanin (black pigment) residue. In this work we develop the chemical imaging methodology to show that organosulfur-Zn complexes are indicators of pheomelanin (red pigment) in extant and fossil soft tissue and that the mapping of these residual biochemical compounds can be used to restore melanin pigment distribution in a 3 million year old extinct mammal species (Apodemus atavus). Synchotron Rapid Scanning X-ray Fluorescence imaging showed that the distributions of Zn and organic S are correlated within this fossil fur just as in pheomelanin-rich modern integument. Furthermore, Zn coordination chemistry within this fossil fur is closely comparable to that determined from pheomelanin-rich fur and hair standards. The non-destructive methods presented here provide a protocol for detecting residual pheomelanin in precious specimens.
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May 2019
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I18-Microfocus Spectroscopy
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Jennifer
Anne
,
Roya A.
Wogelius
,
Nicholas P.
Edwards
,
Arjen
Van Veelen
,
Michael
Buckley
,
William
Sellers
,
Uwe
Bergmann
,
Dimosthenis
Sokaras
,
Roberto
Alonso-Mori
,
Virginia L.
Harvey
,
Victoria M.
Egerton
,
Phillip L.
Manning
Diamond Proposal Number(s):
[9488]
Abstract: Trace element inventories are known to correlate with specific histological structures in bone, reflecting organismal physiology and life histories. By studying trace elements in fossilised bone, particularly in individuals with cyclic bone growth (alternating fast/slow bone deposition), we can improve our understanding of the physiology of extinct organisms. In this study we present the first direct comparison between optical histology (bone tissue identification) and synchrotron-based chemical mapping, quantification, and characterisation of trace elements (biochemistry) within cyclic growth tissues, in this case within bones of a cave hyaena (Crocuta crocuta spelaea). Results show distributions of zinc, an element strongly associated with active ossification and bone growth, correlating with (1) fast-growing tissue of zonal bone (cyclic growth) in an extinct hyaena and (2) secondary osteons (remodelling) in both extant and extinct hyaena. Concentrations and coordination chemistry of zinc within the fossil sample are comparable to those seen in extant bone suggesting that zinc is endogenous to the sample and that the chemistry of bone growth has been preserved for 40 ka. These results demonstrate that the study of trace elements as part of the histochemistry has wide utility for reconstructing growth, diet and other lifestyle factors in archaeological and fossil bone.
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Oct 2018
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I18-Microfocus Spectroscopy
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Fabien
Knoll
,
Luis M.
Chiappe
,
Sophie
Sanchez
,
Russell J.
Garwood
,
Nicholas P.
Edwards
,
Roy A.
Wogelius
,
William I.
Sellers
,
Phillip L.
Manning
,
Francisco
Ortega
,
Francisco J.
Serrano
,
Jesús
Marugán-Lobón
,
Elena
Cuesta
,
Fernando
Escaso
,
Jose Luis
Sanz
Diamond Proposal Number(s):
[11865]
Open Access
Abstract: Fossils of juvenile Mesozoic birds provide insight into the early evolution of avian development, however such fossils are rare. The analysis of the ossification sequence in these early-branching birds has the potential to address important questions about their comparative developmental biology and to help understand their morphological evolution and ecological differentiation. Here we report on an early juvenile enantiornithine specimen from the Early Cretaceous of Europe, which sheds new light on the osteogenesis in this most species-rich clade of Mesozoic birds. Consisting of a nearly complete skeleton, it is amongst the smallest known Mesozoic avian fossils representing post-hatching stages of development. Comparisons between this new specimen and other known early juvenile enantiornithines support a clade-wide asynchronous pattern of osteogenesis in the sternum and the vertebral column, and strongly indicate that the hatchlings of these phylogenetically basal birds varied greatly in size and tempo of skeletal maturation.
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Mar 2018
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[11865]
Abstract: Endochondral ossification is the process by which bone is deposited during development, growth and repair of the skeleton. The regulation of endochondral ossification is extremely important as developmental flaws can result in severe skeletal abnormalities. However, until recently the limitations of available methodologies have restricted our understanding of this fundamental physiological process. The analysis of chemical elements that are intimately associated with discrete biochemical stages of ossification within bone could provide new insight to such processes at the atomic level. In this study we present detailed characterisation of the elemental inventory within actively ossifying bone during development in mice using synchrotron microfocus X-ray techniques. X-ray fluorescence imaging showed differential distributions of Zn, Sr and Ca, which may be correlated with the processes of cartilage replacement (Zn), active ossification (Sr) and fully ossified tissues (Ca). Quantification of these trace elements confirmed their relative distributions. These results represent the first detailed visualisation of local endochondral ossification processes using trace elemental mapping. Such studies have far reaching applications not only in the medical field, but to our understanding of the evolution of the bony skeleton given that trace element inventories have been shown to be preserved through deep time (millions of years).
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Mar 2017
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I18-Microfocus Spectroscopy
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Nicholas
Edwards
,
Arjen
Van Veelen
,
Jennifer
Anné
,
Phillip
Manning
,
Uwe
Bergmann
,
William
Sellers
,
Victoria
Egerton
,
Dimosthenis
Sokaras
,
Roberto
Alonso-Mori
,
Kazumasa
Wakamatsu
,
Shosuke
Ito
,
Roy A.
Wogelius
Diamond Proposal Number(s):
[11865, 12948]
Open Access
Abstract: Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms.
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Sep 2016
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[9488, 8597]
Open Access
Abstract: Bone remodelling is a crucial biological process needed to maintain elemental homeostasis. It is important to understand the trace elemental inventories that govern these processes as malfunctions in bone remodelling can have devastating effects on an organism. In this study, we use a combination of X-ray techniques to map, quantify, and characterise the coordination chemistry of trace elements within the highly remodelled bone tissues of extant and extinct Sirenia (manatees and dugongs). The dense bone structure and unique body chemistry of sirenians represent ideal tissues for studying both high remodelling rates as well as unique fossilisation pathways. Here, elemental maps revealed uncorrelated patterning of Ca and Zn within secondary osteons in both extant and fossil sirenians, as well as elevated Sr within the connecting canals of fossil sirenians. Concentrations of these elements are comparable between extant and fossil material indicating geochemical processing of the fossil bone has been minimal. Zn was found to be bound in the same coordination within the apatite structure in both extant and fossil bone. Accurate quantification of trace elements in extant material was only possible when the organic constituents of the bone were included. The comparable distributions, concentrations, and chemical coordination of these physiologically important trace elements indicate the chemistry of bone remodelling has been preserved for 19 million years. This study signifies the powerful potential of merging histological and chemical techniques in the understanding of physiological processes in both extant and extinct vertebrates.
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Mar 2016
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I18-Microfocus Spectroscopy
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Victoria
Egerton
,
Roy A.
Wogelius
,
Mark A.
Norell
,
Nicholas
Edwards
,
William
Sellers
,
Uwe
Bergmann
,
Dimosthenis
Sokaras
,
Roberto
Alonso-Mori
,
Konstantin
Ignatyev
,
Arjen
Van Veelen
,
Jennifer
Anné
,
Bart
Van Dongen
,
Fabien
Knoll
,
Phillip
Manning
Diamond Proposal Number(s):
[8597, 9488]
Open Access
Abstract: The preservation of fossils reflects the interplay of inorganic and organic chemical processes, which should be clearly differentiated to make interpretations about the biology of extinct organisms. A new coliiformes bird (mouse bird) from the [similar]50 million year old Green River Formation (Wyoming, USA) has here been analysed using synchrotron X-ray fluorescence and environmental scanning electron microscopy with an attached X-ray energy dispersive system (ESEM-EDS). The concentration and distribution of 16 elements (Si, P, S, Cl, K, Ca, Ti, Mg, Fe, Ni, Cu, Zn, As, Br, Ba, Hg) has been mapped for individual points on the sample. S, Cu and Zn map distinctly within visibly preserved feathers and X-ray Absorption Spectroscopy (XAS) shows that S and Cu within the feathers are organically bound in a similar manner to modern feathers. The morphological preservation of the feathers, on both macro- and microscopic scales, is variable throughout the fossil and the differences in the lateral microfacies have resulted in a morphological preservation gradient. This study clearly differentiates endogenous organic remains from those representing exogenous overprinted geochemical precipitates and illustrates the chemical complexity of the overall taphonomic process.
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Jan 2015
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[8597]
Open Access
Abstract: Many exceptionally preserved fossils have long been thought the product of preservation by bacterial autolithification, based largely upon the presence of, micron-sized, 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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Nov 2014
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I18-Microfocus Spectroscopy
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J.
Anne
,
N. P.
Edwards
,
R. A.
Wogelius
,
A. R.
Tumarkin-Deratzian
,
W. I.
Sellers
,
A.
Van Veelen
,
U.
Bergmann
,
D.
Sokaras
,
R.
Alonso-Mori
,
K.
Ignatyev
,
V. M.
Egerton
,
P. L.
Manning
Open Access
Abstract: 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 scanningX-ray fluorescence (SRSXRF) is an elemental mapping technique that uniquely combines high sensitivity (ppm), excellent sample resolution (20100 µm) and the ability to scan large specimens (decimetre scale) approximately 3000 times faster than other mapping techniques. Here, we use SRSXRF combined with microfocus elemental mapping (220 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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Jul 2014
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I18-Microfocus Spectroscopy
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N. P.
Edwards
,
P. L.
Manning
,
U.
Bergmann
,
P. L.
Larson
,
B. E.
Van Dongen
,
W. I.
Sellers
,
S. M.
Webb
,
D.
Sokaras
,
R.
Alonso-Mori
,
K.
Ignatyev
,
H. E.
Barden
,
A.
Van Veelen
,
J.
Anne
,
V. M.
Egerton
,
R. A.
Wogelius
Diamond Proposal Number(s):
[8597]
Open Access
Abstract: Large-scale Synchrotron Rapid Scanning X-ray Fluorescence (SRS-XRF) elemental mapping and X-ray absorption spectroscopy are applied here to fossil leaf material from the ∼50 Mya Green River Formation (USA) in order to improve our understanding of the chemistry of fossilized plant remains. SRS-XRF of fossilized animals has previously shown that bioaccumulated trace metals and sulfur compounds may be preserved in their original distributions and these elements can also act as biomarkers for specific biosynthetic pathways. Similar spatially resolved chemical data for fossilized plants is sparsely represented in the literature despite the multitude of other chemical studies performed. Here, synchrotron data from multiple specimens consistently show that fossil leaves possess chemical inventories consisting of organometallic and organosulfur compounds that: (1) map discretely within the fossils, (2) resolve fine scale biological structures, and (3) are distinct from embedding sedimentary matrices. Additionally, the chemical distributions in fossil leaves are directly comparable to those of extant leaves. This evidence strongly suggests that a significant fraction of the chemical inventory of the examined fossil leaf material is derived from the living organisms and that original bioaccumulated elements have been preserved in situ for 50 million years. Chemical information of this kind has so far been unknown for fossilized plants and could for the first time allow the metallome of extinct flora to be studied.
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Apr 2014
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