Synthetic amphiboles and triple-chain silicates in the system Na(2)O-MgO-SiO(2)-H(2)O: phase characterization, compositional relations and excess H.

Maresch, W. V., Welch, M. D., Gottschalk, M., Ruthmann, W., Czank, M. and Ashbrook, S. E. (2009) Synthetic amphiboles and triple-chain silicates in the system Na(2)O-MgO-SiO(2)-H(2)O: phase characterization, compositional relations and excess H. Mineralogical Magazine, 73 (6). pp. 957-996. DOI 10.1180/minmag.2009.073.6.957.

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The presence of structural OH in amphiboles in excess of the usual two OH per formula has been debated for over 40 years (Gier et al., 1964; Leake et al., 1968). However, the reality of the excess-OH phenomenon is still an open question, because accurate water analyses of amphiboles are rarely available. In this study, we review the data available on the chemically simple synthetic system Na(2)O-MgO-SiO(2)-H(2)O (NMSH) and present new results from NMR, infrared spectroscopy, and X-ray-diffraction that allow re-interpretation of previous studies of NMSH amphiboles along the pseudobinary join between the two end-member compositions Na(2)Mg(6)Si(8)O(22)(OH)(2) and Na(3)Mg(5)Si(8)O(21)(OH)(3). We show that there is extensive solid solution involving excess H at 650-750 degrees C, but also document the presence of a wide miscibility gap below 600 degrees C. This miscibility gap is defined by amphiboles very close to the end-member composition Na(3)Mg(5)Si(8)O(21)(OH)(3) coexisting with amphiboles with compositions near the 'normal' Na(2)Mg(6)Si(8)O(22)(OH)(2) end member. We also report the characterization of triple-chain silicates (TCS) in the NMSH system and their phase relations with NMSH amphiboles. The upper thermal stability field of the key TCS Na(2)Mg(4)Si(6)O(16)(OH)(2) relative to its decomposition to two NMSH amphiboles with a combined equivalent composition has been determined and a pronounced backbend of the transformation boundary documented. Phase relations observed in synthesis experiments suggest that at 550-650 degrees C all TCSs have compositions close to Na(2)Mg(4)Si(6)O(16)(OH)(2). Infrared spectroscopy indicates that the TCS synthesized on this composition, studied in detail here, vary from end-member Na(2)Mg(4)Si(6)O(16)(OH)(2) to binary solid solutions with less than similar to 6 mol.% clinojimthompsonite component. No clear spectroscopic evidence for a 'Drits' component NaMg(4)Si(6)O(15)(OH)(3) (Drits et al., 1975) has been found. Analysis of H(2)O by vacuum extraction and Karl-Fischer titration indicates large excesses of H(2)O in all the TCSs studied here that clearly exceed the amounts expected from (OH) groups alone. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) indicate that this excess H(2)O is structural. We propose that the excess H(2)O is likely to be molecular H(2)O located in the A-site channels. The observed backbend of the triple-chain decomposition curve is in agreement with a reaction involving dehydration and loss of this molecular H(2)O. However, the absolute amount of analysed molecular H(2)O exceeds that expected from the change in Clapeyron slope alone. While demonstrating the reality of excess OH in amphiboles, the evidence presented in this paper also points to interesting avenues for future research on both amphiboles and TCSs, such as understanding the dynamics and enhanced crystal chemistry of excess OH and molecular H(2)O in pyriboles.

Document Type: Article
Keywords: NMSH system amphibole triple-chain silicate excess OH crystal-chemistry mg-cordierite sodium na(namg)mg5si8o22(oh)(2) pressure biopyriboles diffraction transition stability mica
Research affiliation: Kiel University
DOI etc.: 10.1180/minmag.2009.073.6.957
ISSN: 0026-461X
Date Deposited: 22 Dec 2011 05:20
Last Modified: 23 Sep 2019 18:30

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