atom-probe-tomography-analysis-of-exsolved-mineral-phases

Atom Probe Tomography Analysis of Exsolved Mineral Phases

Element diffusion rates and temperature/pressure control a range of fundamental volcanic and metamorphic processes. Such processes are often recorded in ...

University of Alabama

Electron backscatter diffraction (EBSD) is a microscopy technique that reveals in situ crystallographic information. Currently, it is widely used for the characterization of geological materials and in studies of biomineralization. Here, we analyze high resolution EBSD data from biogenic calcite in two mollusk taxa, Concholepas and Haliotis, previously used in the understanding of complex biomineralization and paleoenvironmental studies. Results indicate that Concholepas has less ordered prisms than in Haliotis, and that in Concholepas the level of order is not homogenous in different areas of the shell. Overall, the usefulness of data integration obtained from diffraction intensity and crystallographic orientation maps, and corresponding pole figures, is discussed as well as its application to similar studies.

High resolution electron backscatter diffraction (EBSD) data from calcite biominerals in recent gastropod shells.

Brachiopods are still one of the least studied groups of organisms in terms of biomineralization despite recent studies indicating the presence of highly complex biomineral structures, particularly in taxa with calcitic shells. Here, we analyze the nanostructure of calcite biominerals, fibers and semi-nacre tablets, in brachiopod shells by high-resolution scanning electron microscopy (SEM) and atomic force microscopy (AFM). We demonstrate that basic mechanisms of carbonate biomineralization are not uniform within the phylum, with semi-nacre tablets composed of spherical aggregates with sub-rounded granules and fibers composed of large, triangular or rod-like particles composed of small sub-rounded granules (40-60 nm). Additionally, proteinaceous envelopes surrounding calcite fibers have been shown for the first time to have a dual function: providing a micro-environment in which granules are produced and acting as the organic template for particle orientation as fiber components. In summary, these new findings in brachiopod shells reveal a complex and distinctive style of biomineralization among carbonate-producing organisms.

Biogenic calcite granules--are brachiopods different?

Marine macroinvertebrates are ideal sentinel organisms to monitor rapid environmental changes associated with climatic phenomena. These organisms build up protective exoskeletons incrementally by biologically-controlled mineralization, which is deeply rooted in long-term evolutionary processes. Recent studies relating potential rapid environmental fluctuations to climate change, such as ocean acidification, suggest modifications on carbonate biominerals of marine invertebrates. However, the influence of known, and recurrent, climatic events on these biological processes during active mineralization is still insufficiently understood. Analysis of Peruvian cockles from the 1982-83 large magnitude El Niño event shows significant alterations of the chemico-structure of carbonate biominerals. Here, we show that bivalves modify the main biomineralization mechanism during the event to continue shell secretion. As a result, magnesium content increases to stabilize amorphous calcium carbonate (ACC), inducing a rise in Mg/Ca unrelated to the associated increase in sea-surface temperature. Analysis of variations in Sr/Ca also suggests that this proxy should not be used in these bivalves to detect the temperature anomaly, while Ba/Ca peaks are recorded in shells in response to an increase in productivity, or dissolved barium in seawater, after the event. Presented data contribute to a better understanding of the effects of abrupt climate change on shell biomineralization, while also offering an alternative view of bivalve elemental proxy reconstructions. Furthermore, biomineralization changes in mollusk shells can be used as a novel potential proxy to provide a more nuanced historical record of El Niño and similar rapid environmental change events.

El Niño impact on mollusk biomineralization-implications for trace element proxy reconstructions and the paleo-archeological record.

We studied the population dynamics and parasite load of the foraminifer Cibicides antarcticus on its host the Antarctic scallop Adamussium colbecki from three localities differing by sea ice cover within western McMurdo Sound, Ross Sea, Antarctica: Explorers Cove, Bay of Sails and Herbertson Glacier. We also estimated CaCO3 biomass and annual production for both species. Cibicides populations varied by locality, valve type, and depth. Explorers Cove with multiannual sea ice had larger populations than the two annual sea ice localities, likely related to differences in nutrients. Populations were higher on Adamussium top valves, a surface that is elevated above the sediment. Depth did not affect Cibicides distributions except at Bay of Sails. Cibicides parasite load (the number of complete boreholes in Adamussium valves) varied by locality between 2% and 50%. For most localities the parasite load was < 20%, contrary to a previous report that ~50% of Cibicides were parasitic. The highest and lowest parasite load occurred at annual sea ice localities, suggesting that sea ice condition is not important. Rather, the number of adults that are parasitic could account for these differences. Cibicides bioerosion traces were categorized into four ontogenetic stages, ranging from newly attached recruits to parasitic adults. These traces provide an excellent proxy for population structure, revealing that Explorers Cove had a younger population than Bay of Sails. Both species are important producers of CaCO3. Cibicides CaCO3 biomass averaged 47-73 kg ha(-1) and Adamussium averaged 4987-6806 kg ha(-1) by locality. Annual production rates were much higher. Moreover, Cibicides represents 1.0-2.3% of the total host-parasite CaCO3 biomass. Despite living in the coldest waters on Earth, these species can contribute a substantial amount of CaCO3 to the Ross Sea and need to be incorporated into food webs, ecosystem models, and carbonate budgets for Antarctica.

Population Dynamics and Parasite Load of a Foraminifer on Its Antarctic Scallop Host with Their Carbonate Biomass Contributions.

Our understanding of the evolutionary transitions leading to the modern endothermic state of birds and mammals is incomplete, partly because tools available to study the thermophysiology of extinct vertebrates are limited. Here we show that clumped isotope analysis of eggshells can be used to determine body temperatures of females during periods of ovulation. Late Cretaceous titanosaurid eggshells yield temperatures similar to large modern endotherms. In contrast, oviraptorid eggshells yield temperatures lower than most modern endotherms but ∼ 6 °C higher than co-occurring abiogenic carbonates, implying that this taxon did not have thermoregulation comparable to modern birds, but was able to elevate its body temperature above environmental temperatures. Therefore, we observe no strong evidence for end-member ectothermy or endothermy in the species examined. Body temperatures for these two species indicate that variable thermoregulation likely existed among the non-avian dinosaurs and that not all dinosaurs had body temperatures in the range of that seen in modern birds.

Isotopic ordering in eggshells reflects body temperatures and suggests differing thermophysiology in two Cretaceous dinosaurs.

Atom probe tomography (APT) combines the highest spatial resolution with chemical data at atomic scale for the analysis of materials. For geological specimens, the process of field evaporation and molecular ion formation and interpretation is not yet entirely understood. The objective of this study is to determine the best conditions for the preparation and analysis by APT of carbonate minerals, of great importance in the interpretation of geological processes, focusing on the bulk chemical composition. Results show that the complexity of the mass spectrum is different for calcite and dolomite and relates to dissimilarities in crystalochemical parameters. In addition, APT bulk chemistry of calcite closely matches the expected stoichiometry but fails to provide accurate atomic percentages for elements in dolomite under the experimental conditions evaluated in this work. For both calcite and dolomite, APT underestimates the amount of oxygen based on their chemical formula, whereas it is able to detect small percentages of elemental substitutions in crystal lattices. Overall, our results demonstrate that APT of carbonate minerals is possible, but further optimization of the experimental parameters are required to improve the use of atom probe tomography for the correct interpretation of mineral geochemistry. 

Atom probe tomography (APT) of carbonate minerals.

The structure and composition of the eggshells of two commercial species (guinea fowl and greylag goose) have been studied. Thin sections and scanning electron microcopy show the similarity of the overall structure, but the relative thickness of the layers differs in these two taxa. Atomic force microscopy shows that the different layers are composed of rounded, heterogeneous granules, the diameter of which is between 50 and 100 nm, with a thin cortex. Infrared data and thermogravimetric analyses show that both eggshells are made of calcite, but differing on the quality and quantity when the organic component is considered. Chemical maps show that chemical element distribution is not uniform within a sample, and differs between the species, but with low magnesium content. Electron back scattered diffraction confirms the eggshells are calcite, but the microtexture strongly differs between the two species. Based on the chemical-structural differences, a species-specific biological control on the biomineralization is found, despite the rapid formation of an eggshell. Overall results indicate that to estimate the quality of eggshells, such as resistance to breakage, is not a straightforward process because of the high complexity of avian eggshell biomineralization.

Comparison of the structure, crystallography and composition of eggshells of the guinea fowl and graylag goose.

The current work represents a distinctive study about the biomineral properties of exceptionally good preserved skeletons of Calceola sandalina from the Middle Devonian of Couvin (Belgium), Smara (Morocco) and (Algeria) and their relation in the evolution of biomineralization of cnidarians. Structural and crystallographic analyses of the skeletons have been done by petrographic microscopy, electron scanning microscopy (SEM), atomic force microscopy (AFM), electron backscatter diffraction (EBSD), computer-integrated polarization microscopy (CIP) and electron microprobe analysis (EMPA). Calceola skeletons have many similarities with other cnidarians, mainly with other Palaeozoic corals as Syringoporicae: The microcrystals are composed of co-oriented nanocrystals that remind to mesocrystals, suggesting a biocrystallization process by particle attachment (CPA). The relationship between the nanocrystals and microcrystals suggest a growth mode similar to mineral bridges. A similar model was described for Syringoporicae corals (Tabulata) and it is similar to the coordinated-growth mode described in scleractinians and molluscs. Calceola skeletons show also a convergent structure with scleractinian forming Rapid Accretion Deposits (RAD), which share some structural and chemical properties. These evidences suggest analogous processes of biomineralization derived from a stem group of cnidarians. The results of this paper highlight the value of biomineralization studies in fossil organisms to understand the evolution of biomineralization mechanism through Phanerozoic.

Analogous biomineralization processes between the fossil coral Calceola sandalina (Rugosa, Devonian) and other Recent and fossil cnidarians.

Marine CO seeps allow the study of the long-term effects of elevated pCO (ocean acidification) on marine invertebrate biomineralization. We investigated the effects of ocean acidification on shell composition and structure in four ecologically important species of Mediterranean gastropods (two limpets, a top-shell snail, and a whelk). Individuals were sampled from three sites near a volcanic CO seep off Vulcano Island, Italy. The three sites represented ambient (8.15pH), moderate (8.03pH) and low (7.73pH) seawater mean pH. Shell mineralogy, microstructure, and mechanical strength were examined in all four species. We found that the calcite/aragonite ratio could vary and increased significantly with reduced pH in shells of one of the two limpet species. Moreover, each of the four gastropods displayed reductions in either inner shell toughness or elasticity at the Low pH site. These results suggest that near-future ocean acidification could alter shell biomineralization and structure in these common gastropods.

Effects of ocean acidification on the shells of four Mediterranean gastropod species near a CO seep.

Avian eggshells are composed of several layers made of organic compounds and a mineral phase (calcite), and the general structure is basically the same in all species. A comparison of the structure, crystallography, and chemical composition shows that despite an overall similarity, each species has its own structure, crystallinity, and composition. Eggshells are a perfect example of the crystallographic versus biological concept of the formation and growth mechanisms of calcareous biominerals: the spherulitic-columnar structure is described as "a typical case of competitive crystal growth", but it is also said that the eggshell matrix components regulate eggshell mineralization. Electron back scattered diffraction (EBSD) analyses show that the crystallinity differs between different species. Nevertheless, the three layers are composed of rounded granules, and neither facets nor angles are visible. In-situ analyses show the heterogeneous distribution of chemical elements throughout the thickness of single eggshell. The presence of organic matrices other than the outer and inner membranes in eggshells is confirmed by thermograms and infrared spectrometry, and the differences in quality and quantity depend on the species. Thus, as in other biocrystals, crystal growth competition is not enough to explain these differences, and there is a strong biological control of the eggshell secretion.

Article	Year
High resolution electron backscatter diffraction (EBSD) data from calcite biominerals in recent gastropod shells. Micron (Oxford, England : 1993)\| PubMed ID: 21130663	2011
Biogenic calcite granules--are brachiopods different? Micron (Oxford, England : 1993)\| PubMed ID: 23026148	2013
El Niño impact on mollusk biomineralization-implications for trace element proxy reconstructions and the paleo-archeological record. PloS one\| PubMed ID: 23405078	2013
Population Dynamics and Parasite Load of a Foraminifer on Its Antarctic Scallop Host with Their Carbonate Biomass Contributions. PloS one\| PubMed ID: 26186724	2015
Isotopic ordering in eggshells reflects body temperatures and suggests differing thermophysiology in two Cretaceous dinosaurs. Nature communications\| PubMed ID: 26462135	2015
Atom probe tomography (APT) of carbonate minerals. Micron (Oxford, England : 1993)\| PubMed ID: 26519815	2016
Comparison of the structure, crystallography and composition of eggshells of the guinea fowl and graylag goose. Zoology (Jena, Germany)\| PubMed ID: 26711013	2016
Analogous biomineralization processes between the fossil coral Calceola sandalina (Rugosa, Devonian) and other Recent and fossil cnidarians. Journal of structural biology\| PubMed ID: 27327265	2016
Effects of ocean acidification on the shells of four Mediterranean gastropod species near a CO seep. Marine pollution bulletin\| PubMed ID: 28823551	2017
Biomineralization in modern avian calcified eggshells: similarity versus diversity. Connective tissue research\| PubMed ID: 29745812	2018

Alberto Perez-Huerta

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