Characterization of polysomatism in biopyriboles: Double-/triple-chain lamellar intergrowths

Abstract

As a first step towards accurate quantification of the polysomatic states of biopyriboles, we have studied the polysomatic transformation between amphibole and hydrous triple-chain silicate (TCS) in the synthetic system Na₂O-MgO-SiO₂-H₂O (NMSH). The reaction is: 4Na₂Mg₄Si₆O₁₆(OH)₂ TCS ⇔ 3Na_2.67Mg_5.33Si₈O_21.33(OH)_2.67. Amphibole We have characterised a polysomatic intergrowth of amphibole and TCS (synthesized at 2 kbar/(653° C) by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), infrared spectroscopy and ²⁹Si magic-angle-spinning (MAS) NMR spectroscopy. The sample is a fine-scale lamellar intergrowth of double- and triple-chain structures; lamellae are 27 Å to hundreds of Ångströms wide. The ²⁹Si MAS NMR spectrum of the intergrowth is explicitly a superposition of the individual amphibole and TCS spectra. By ensuring that the recycle delay time used considers the longest spin-lattice relaxation time (ca. 900 s), the relative amounts of double- and triple-chain structures can be quantified by simple deconvolution of the spectrum. The relative amounts of double- and triple-chain structures are 42 ± 5 and 58 ± 5 mol%, respectively. With regard to quantifying populations of chain multiplicities in biopyriboles, we believe that ²⁹Si NMR is more accurate than the conventional HRTEM fringe-counting method (Maresch and Czank 1983, 1988), and is far superior to XRD and infrared spectroscopy, which suffer from high sensitivity to particle size and calibration problems. ²⁹Si MAS NMR can provide an accurate means of monitoring the progress of polysomatic reactions in biopyriboles. It is likely to be most effective for samples containing only a few different chain multiplicities (e.g. m = 1, 2, 3 and perhaps 4), such as occur in natural pyroxenes and amphiboles.