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Differences in chemical thickness of grain and phase boundaries: an atom probe tomography study of experimentally deformed wehrlite

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Abstract

The chemical widths of grain and phase boundaries in deformed wehrlite (olivine–clinopyroxene; Ol–Cpx) aggregates are characterized by atom probe tomography (APT), a (laser-assisted) field evaporation technique employing time-of-flight mass spectrometry. The wehrlite was deformed to high finite strain in diffusion creep: The effective viscosity measured for the wehrlite is approximately an order of magnitude lower than that of either end-member aggregate; further, phase ordering, in which the spatial density of Ol–Cpx phase boundaries increases with accumulated strain, characterizes the deformation (Zhao et al. in Earth Planet Sci Lett 517:83–94, 2019). The mechanical results imply that the transport properties of the phase boundaries—dictated by their structure and composition—differ from those of grain boundaries. Our APT data show that, indeed, the chemical widths of crystalline Ol–Cpx phase boundaries—3.1–6.6 nm, depending on the element used for their characterization—are up to a factor of two greater than the chemical widths of crystalline Ol–Ol and Cpx–Cpx grain boundaries. Careful statistical analyses of the APT data reveal that the near-boundary compositional profiles of the presented Ol–Cpx phase boundary are consistent with—indeed, evidence for—the rheological model in which diffusion creep is rate-limited by the (mechanism-required) interfacial reactions at the Ol–Cpx phase boundaries. Such an analysis is unavailable by current electron beam/X-ray spectrometry approaches, which have not the requisite spatial precision. APT application to nanometer-scale problems in silicate petrology is challenging, particularly because signal overlap is caused by the evaporation of polyion species. We carefully outline the procedures used to acquire and discriminate the data in order to address the challenges of signal overlap.

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Acknowledgements

Prof. Greg Hirth (Brown University) offered lively discussion of aspects of mechanical properties theory. Joseph Bunton (Cameca Instruments, Madison, WI) helped us understand aspects of laser–solid interaction. This work was carried out in part at (a) the Center for Nanoscale Systems, Harvard University (National Science Foundation award number 1541959), and (b) the Central Analytical Facility supported by the University of Alabama. We happily acknowledge very helpful formal reviews by Drs. Steve Reddy and Sandra Piazolo and journal editor Larissa Dobrzhinetskaya. This research was supported financially, in part, through grants from the National Science Foundation Division of Earth Sciences (EAR-1144668, Program in Petrology and Geochemistry; EAR-1620474, Program in Geophysics).

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Authors and Affiliations

  1. Department of Earth, Environmental and Planetary Sciences, Brown University, Providence, RI, 02912, USA

    Joseph T. Cukjati, Reid F. Cooper, Stephen W. Parman & Ningli Zhao

  2. Center for Nanoscale Systems, Harvard University, Cambridge, MA, 02138, USA

    Austin J. Akey

  3. Department of Geological Sciences, University of Alabama, Tuscaloosa, AL, 35487, USA

    Fernando A. T. P. Laiginhas

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  1. Joseph T. Cukjati
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269_2019_1045_MOESM1_ESM.png

Supplementary Figure A: Proxigram and 1-D analyses of major and minor element chemistry near the olivine–clinopyroxene phase boundary. Proxigram based on a Ca2+ isosurface created with a 3-nm grid-size smoothing. Delocalization parameters are x = 3.0 nm, y = 3.0 nm and z = 1.5 nm. The upper-left graphs represent total detected atomic species (PNG 384 kb)

269_2019_1045_MOESM2_ESM.png

Supplementary Figure B: Proxigram and 1-D analyses of trace element chemistry near the olivine–clinopyroxene phase boundary. Proxigram based on a Ca2+ isosurface created with a 3-nm grid-size smoothing. Delocalization parameters are x = 3.0 nm, y = 3.0 nm and z = 1.5 nm (PNG 426 kb)

269_2019_1045_MOESM3_ESM.png

Supplementary Figure C: Proxigram and 1-D analyses of major and minor element chemistry near the olivine–olivine grain boundary. Proxigram based on a Ca2+ isosurface created with a 5-nm grid-size smoothing. Delocalization parameters are x = 3.0 nm, y = 3.0 nm and z = 1.5 nm. The upper-left graphs represent total detected atomic species (PNG 397 kb)

269_2019_1045_MOESM4_ESM.png

Supplementary Figure D: Proxigram and 1-D analyses of trace element chemistry near the olivine–olivine phase boundary. Proxigram based on a Ca2+ isosurface created with a 5-nm grid-size smoothing. Delocalization parameters are x = 3.0 nm, y = 3.0 nm and z = 1.5 nm (PNG 414 kb)

269_2019_1045_MOESM5_ESM.png

Supplementary Figure E: 1-D analyses of major and minor element chemistry near the clinopyroxene–clinopyroxene grain boundary. Insufficient chemical gradients exist for proxigram calculations at this interface. Delocalization parameters are x = 3.0 nm, y = 3.0 nm and z = 1.5 nm. The upper-left graph represents total detected atomic species (PNG 273 kb)

269_2019_1045_MOESM6_ESM.png

Supplementary Figure F: 1-D analyses of trace element chemistry near the clinopyroxene–clinopyroxene grain boundary. Insufficient chemical gradients exist for proxigram calculations at this interface. Delocalization parameters are x = 3.0 nm, y = 3.0 nm and z = 1.5 nm (PNG 289 kb)

Supplementary Figure G: Mass spectrum for the Ol–Ol tip. Full spectrum is available in Table 2 (PNG 158 kb)

Supplementary Figure H: Mass spectrum for the Ol–Cpx tip. Full spectrum is available in Table 2 (PNG 162 kb)

Supplementary Figure I: Mass spectrum for the Cpx–Cpx tip. Full spectrum is available in Table 2 (PNG 164 kb)

269_2019_1045_MOESM10_ESM.png

Supplementary Figure J: Selected APT analytical reconstructions from the Cpx–Cpx boundary. The 3-D reconstruction is oriented with the vector normal to the grain boundary within the plane of the page. Al and Ca are enriched at the Cpx–Cpx boundary (PNG 729 kb)

Supplementary material 11 (DOCX 14 kb)

Supplementary material 12 (DOCX 15 kb)

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Cukjati, J.T., Cooper, R.F., Parman, S.W. et al. Differences in chemical thickness of grain and phase boundaries: an atom probe tomography study of experimentally deformed wehrlite. Phys Chem Minerals 46, 845–859 (2019). https://doi.org/10.1007/s00269-019-01045-x

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