Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals

X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demon...

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Main Authors: DeVol, R., Metzler, R., Kabalah-Amitai, L., Pokroy, B., Politi, Y., Gal, A., Addadi, L., Weiner, S., Fernandez-Martinez, A., Demichelis, Raffaella, Gale, Julian, Ihli, J., Meldrum, F., Blonsky, A., Killian, C., Salling, C., Young, A., Marcus, M., Scholl, A., Doran, A., Jenkins, C., Bechtel, H., Gilbert, P.
Format: Journal Article
Published: American Chemical Society 2014
Online Access:http://hdl.handle.net/20.500.11937/14437
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author DeVol, R.
Metzler, R.
Kabalah-Amitai, L.
Pokroy, B.
Politi, Y.
Gal, A.
Addadi, L.
Weiner, S.
Fernandez-Martinez, A.
Demichelis, Raffaella
Gale, Julian
Ihli, J.
Meldrum, F.
Blonsky, A.
Killian, C.
Salling, C.
Young, A.
Marcus, M.
Scholl, A.
Scholl, A.
Doran, A.
Jenkins, C.
Jenkins, C.
Bechtel, H.
Gilbert, P.
author_facet DeVol, R.
Metzler, R.
Kabalah-Amitai, L.
Pokroy, B.
Politi, Y.
Gal, A.
Addadi, L.
Weiner, S.
Fernandez-Martinez, A.
Demichelis, Raffaella
Gale, Julian
Ihli, J.
Meldrum, F.
Blonsky, A.
Killian, C.
Salling, C.
Young, A.
Marcus, M.
Scholl, A.
Scholl, A.
Doran, A.
Jenkins, C.
Jenkins, C.
Bechtel, H.
Gilbert, P.
author_sort DeVol, R.
building Curtin Institutional Repository
collection Online Access
description X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment.
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spelling curtin-20.500.11937-144372017-09-13T14:04:53Z Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals DeVol, R. Metzler, R. Kabalah-Amitai, L. Pokroy, B. Politi, Y. Gal, A. Addadi, L. Weiner, S. Fernandez-Martinez, A. Demichelis, Raffaella Gale, Julian Ihli, J. Meldrum, F. Blonsky, A. Killian, C. Salling, C. Young, A. Marcus, M. Scholl, A. Scholl, A. Doran, A. Jenkins, C. Jenkins, C. Bechtel, H. Gilbert, P. X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment. 2014 Journal Article http://hdl.handle.net/20.500.11937/14437 10.1021/jp503700g American Chemical Society restricted
spellingShingle DeVol, R.
Metzler, R.
Kabalah-Amitai, L.
Pokroy, B.
Politi, Y.
Gal, A.
Addadi, L.
Weiner, S.
Fernandez-Martinez, A.
Demichelis, Raffaella
Gale, Julian
Ihli, J.
Meldrum, F.
Blonsky, A.
Killian, C.
Salling, C.
Young, A.
Marcus, M.
Scholl, A.
Scholl, A.
Doran, A.
Jenkins, C.
Jenkins, C.
Bechtel, H.
Gilbert, P.
Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals
title Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals
title_full Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals
title_fullStr Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals
title_full_unstemmed Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals
title_short Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals
title_sort oxygen spectroscopy and polarization-dependent imaging contrast (pic)-mapping of calcium carbonate minerals and biominerals
url http://hdl.handle.net/20.500.11937/14437