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American Mineralogist; March 1999; v. 84; no. 3; p. 325-332
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"Cs-tetra-ferri-annite; high-pressure and high-temperature behavior of a potential nuclear waste disposal phase

Paola Comodi, Pier Francesco Zanazzi, Zdenek Weiss, Milan Rieder, and Milan Drabek

Universita di Perugia, Dipartimento di Scienze della Terra, Perugia, Italy

Structure deformations induced by pressure and temperature in synthetic "Cs-tetra-ferri-annite" 1M [Cs (sub 1.78) (Fe (super 2+) (sub 5.93) Fe (super 3+) (sub 0.07) )(Si (sub 6.15) Fe (super 3+) (sub 1.80) Al (sub 0.05) )O 20 (OH) 4 ], space group C2/m, were analyzed to investigate the capability of the mica structure to store the radiogenic isotopes 135 Cs and 137 Cs. "Cs-tetra-ferri-annite" is not a mineral name, but for the sake of brevity is used here to designate a synthetic analog of the mineral tetra-ferri-annite. The bulk modulus and its pressure derivative determined by fitting the unit-cell volumes between 0 and 47 kbar to a third-order Birch-Murnaghan equation of state are K 0 = 257(8) kbar and K' 0 = 21(1), respectively. Between 23 degrees C and 582 degrees C, the a and b lattice parameters remain essentially unchanged, but the thermal expansion coefficient of the c axis is alpha c = 3.12(9) X 10 (super -5) degrees C (super -1) . High pressure (P) and high temperature (T) produce limited internal strain in the structure. The tetrahedral rotation angle, alpha , is very small and does not change significantly throughout the P and T range investigated. Above 450 degrees C in air, "Cs-tetra-ferri-annite" underwent an oxidation of octahedral iron in the M2cis site, balanced by the loss of H and shown by a decrease of the unit-cell volume. Independent isobaric data on thermal expansion and isothermal compressibility data define the "geometric" equation of state for "Cs-tetra-ferri-annite": V/V 0 = 1+3.0(1) 10 (super -5) T - 2.68(9) 10 (super -3) P+2.0(2) X 10 (super -5) P 2 where T is in degrees Celsius, P is in kilobars. The alpha /beta ratio of about 12 bar/ degrees C indicate that the cell volume of "Cs-tetra-ferri-annite" remains unchanged under geothermal gradients of approximately 23 degrees C/km. On the whole, the data confirm that the structure of "Cs-tetra-ferri-annite" may be a suitable candidate for the storage of large ions, such as Cs in the interlayer and should be considered as a potential Synroc component.

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