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Stationary and mobile hydrogen defects in potassium feldspar

Kronenberg, Andreas K. and Yund, Richard A. and Rossman, George R. (1996) Stationary and mobile hydrogen defects in potassium feldspar. Geochimica et Cosmochimica Acta, 60 (21). pp. 4075-4094. ISSN 0016-7037. https://resolver.caltech.edu/CaltechAUTHORS:20130416-152200746

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Abstract

Hydrogen defects in adularia from Kristallina, Switzerland (Or90.2 Ab8.7 An0.0 Cs1.1) have been investigated by examining their vibrational modes in the infrared and near-infrared, and by measuring rates of hydrogen loss and hydrogen gain at elevated temperatures. Principal absorption bands exhibited by adularia at wavenumbers of 362 and 345.5 mm^(−1) (corresponding to O-H stretching modes) are strongly dichroic, with maximum and minimum absorptivities measured for vibrations α (E at 5° to a) and β (E at 5° to c^∗), respectively, whereas bands at 328 and 309 mm^(−1) are more nearly isotropic. Similarly, near-infrared bands at 525 and 513 mm^(−1) (associated with combination H-OH bend, O-H stretch modes) exhibit maximum peak heights for α while a lesser band at 475 mm^(−1) appears to be nearly isotropic. Comparison of fundamental and combination band intensities reveal that molecular water is the predominant hydrogen-bearing species, consistent with previous results for microcline and orthoclase crystals in which H_2O substitutes for K. However, differences in magnitude of fundamental and combination band polarizations suggest multiple defect sites or potentially a secondary population of hydroxyl defects. Rates at which these defects can be eliminated from samples annealed in air at temperatures T from 500° to 900°C are much faster than those predicted by oxygen mobilities, yielding diffusivities of D[/_s]=6.2x10^(-4)exp ( -l72 ± 15[^(kJ)/mol))/RT indistinguishable from those reported for proton interstitials in quartz. Dissociation of stationary molecular water defects to mobile proton interstitials which leave crystal interiors requires that oxygen defects are left behind. Hydrogen defects can be added to adularia crystals annealed at elevated water pressures (corresponding to H_2O fugacities of 412 and 1710 MPa and H_2 fugacities up to 174 MPa), again at rates that exceed oxygen mobilities. In addition, significant redistribution amongst sites is suggested by changes in band character and polarization. Neither Fe nor other multivalent impurities are sufficiently abundant to accommodate local charge balance upon the loss or gain of protons and other mechanisms of internal adjustment are required.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/S0016-7037(96)00249-9DOIUNSPECIFIED
http://www.sciencedirect.com/science/article/pii/S0016703796002499PublisherUNSPECIFIED
ORCID:
AuthorORCID
Rossman, George R.0000-0002-4571-6884
Additional Information:© 1996 Elsevier Science Ltd. Received October 6, 1994; accepted in revised form June 27, 1996. This study benefitted significantly from discussions with J. R. Farver, J. Tullis, J. R. Goldsmith, and S. H. Kirby. Constructive reviews of the manuscript were provided by R. C. Burruss, C. M. Graham, G. E. Harlow, and J. S. Huebner. Special thanks go to J. T. Armstrong and R. Guillemette for providing first rate microprobe analyses of Kristallina adularia, including determinations of its major element composition and trace element concentrations. We thank D. Sykes for obtaining several near-IR spectra, and G. Carpenter for assisting us with the numerical (SHELXTL) structure program. The American Museum of Natural History, New York kindly provided the crystal of adularia used in this study. Funding in part was provided by NSF grant EAR 9218980 to G. R. Rossman. Editorial handling: R. C. Burruss.
Funders:
Funding AgencyGrant Number
NSFEAR-9218980
Issue or Number:21
Record Number:CaltechAUTHORS:20130416-152200746
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130416-152200746
Official Citation:Andreas K. Kronenberg, Richard A. Yund, George R. Rossman, Stationary and mobile hydrogen defects in potassium feldspar, Geochimica et Cosmochimica Acta, Volume 60, Issue 21, November 1996, Pages 4075-4094, ISSN 0016-7037, 10.1016/S0016-7037(96)00249-9. (http://www.sciencedirect.com/science/article/pii/S0016703796002499)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:37976
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:16 Apr 2013 22:47
Last Modified:03 Oct 2019 04:53

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