Abstract
Serpentine minerals exert important controls on the physical properties
of ultramafic rocks and have the potential to influence deformation
phenomena in fault zones and to control the release of water in
subducted slabs. Sheet serpentine generally, and lizardite and amesite
specifically, can adopt alternative crystallographic stacking
arrangements called polytypes. Polytypism has been extensively studied
in fully ordered crystals, but it remains largely enigmatic in the more
common semi-disordered crystals that in long-range analyses such as
X-ray diffraction only exhibit random combinations of 0b and ±1/3b
interlayer shifts. To date, atomic-resolution imaging to identify
locally ordered polytypes has been precluded by the beam-sensitive
nature of this hydrous magnesium silicate mineral. Here, we employed
low-dose high-angle annular dark-field scanning transmission electron
microscopy (HAADF-STEM) to study the polytypic structure of
semi-disordered lizardite and amesite. Because the electron dose was as
low as ~6000 e-/Å 2 , it was possible to directly
resolve oxygen atomic columns and all the cations with a resolution of
~1 Å and reveal the short-range order. For lizardite, we
identified long-period non-standard polytypes, including examples with
3, 4, 8 and 9 layers stemming from the ordering of the octahedral tilt
along the a-axis. For amesite, we found short-range ordered polytypes
with periodicities of up to 42 Å stemming from the ordering of
interlayer shifts along the b-axis. The resolution was sufficient to
determine the relative abundance of 6R 2 , 6R 1 , 2H 1 and 2H 2
polytypes in amesite to be 46.1%, 29.6%, 7.7% and 1.9% respectively.
This is contrary to the expectation that the most common form of amesite
is the 2H 2 polytype, which may be more likely to form macroscopic
crystals suitable for conventional X-ray diffraction-based study. We
conclude that HAADF-STEM methods open the way for characterization of
beam sensitive minerals and to resolve the structural details of less
well ordered (but possibly more abundant) minerals at unit-cell scale.