Structural, textural, and chemical controls on the OH stretching vibrations in serpentine-group minerals

Abstract

The OH stretching vibrational properties of eight serpentine samples from veins of the New Caledonian ophiolite have been investigated by Fourier-transform infrared spectroscopy (FTIR) in the mid-infrared and near-infrared ranges and by Raman spectroscopy. The samples were selected for their monophasic composition (Lz: lizardite; Ctl: chrysotile; and Atg: antigorite) making them representative of the three serpentine species. Comparison of fundamental and overtone spectra allowed us to interpret most of the observed bands and to propose consistent spectral decomposition in individual components. The OH stretching bands related to intrinsic vibrational properties of the minerals are distinguished from those associated with chemical substitutions in octahedral sites (mainly Fe and Ni for Mg substitutions). Observations made on the most symmetric Lz are consistent with previous interpretations and underline the effect of macroscopic parameters on OH stretching bands in the FTIR spectra. The major importance of the distribution of OH bond lengths in the broadening of the vibrational signals of the less symmetric and more distorted Atg is confirmed. The combination of the three spectroscopic methods makes it possible to unravel the occurrence of two different types of interlayer OH environments in Ctl nanotubes. One corresponds to the features observed at 3684 and 7171 cm−1 in the fundamental and overtone spectra, respectively, and is similar to the local OH environment observed in Lz. The other corresponds to broader signals observed at 3693 and 7200 cm−1 in the fundamental and overtone spectra, respectively. It reflects a distribution of OH bond lengths likely related to local structural misfits between adjacent layers in the tubular structure of Ctl.