Letter. Pressure-induced stabilization of ordered paranatrolite: A new insight into the paranatrolite controversy
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Abstract
The origin and stability of paranatrolite (approximate formula Na16-xCaxAl16+xSi24-xO80·24H2O), a naturally occurring zeolite with the natrolite topology, has long been debated, with its detailed structure unknown. When taken from an aqueous environment and exposed to the atmosphere, paranatrolite is reported to irreversibly lose water and transform to gonnardite/tetranatrolite, Na16-xCaxAl16+xSi24-xO80·nH2O. Since the latter has a disordered Al/Si distribution over the framework tetrahedral sites, it is believed the same is true for paranatrolite. Natrolite itself (Na16Al16Si24O80·16H2O) has Al/Si ordering, and as recently shown, undergoes a reversible volume expansion (~2.5%) due to pressure-induced hydration (PIH) above 1.2 GPa to a superhydrated phase (Na16Al16Si24O80·32H2O). During this process, an intermediate phase with an even larger volume expansion of ~7.0% has been detected in a narrow pressure range near 1.0 GPa. We report here that this intermediate phase has a unit-cell compatible with the one reported for paranatrolite at ambient conditions with the same 24 water molecules per formula unit and propose that it is paranatrolite with an ordered Al/Si distribution. An unusual watersodium chain is observed in the ordered paranatrolite structure: a sevenfold coordination of sodium cations provided by alternating two water bridges along the expanded elliptical channels. The density of the ordered paranatrolite is lower than those of the 16 and 32 water phases, with its channel openings far more circular than in the low- and high-pressure analogs. The atomistic details of the ordered paranatrolite provide a structural model for the naturally occurring paranatrolite and a complete understanding of this intriguing pressure-volume-hydration mechanism in natrolite, demonstrating the unique role of pressure in controlling the chemistry of microporous materials.
© 2015 by Walter de Gruyter Berlin/Boston
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Articles in the same Issue
- Contact metamorphism of the White Mountain Peak metavolcanic complex, eastern California
- Structure and luminescence characteristics of quartz from pegmatites
- Evidence for monazite-, barite-, and AgMnO4 (distorted barite)-type structures of CaSO4 at high pressure and temperature
- The “template” effect of the extra-framework content on zeolite compression: The case of yugawaralite
- The influence of OH in coesite on the kinetics of the coesite-quartz phase transition
- First-principles study of hydrogen bond symmetrization of phase D under high pressure
- First-principles study of OH-stretching modes in kaolinite, dickite, and nacrite
- A systematic study of OH in hydrous wadsleyite from polarized FTIR spectroscopy and single-crystal X-ray diffraction: Oxygen sites for hydrogen storage in Earthʼs interior
- Determination of the content and distribution of fixed ammonium in illite-smectite using a modified X-ray diffraction technique: Application to oil source rocks of western Greenland
- Determination of defect structures in kaolin minerals by high-resolution transmission electron microscopy (HRTEM)
- Mössbauer spectroscopy of omphacite and garnet pairs from eclogites: Application to geothermobarometry
- Allanite and epidote weathering at the Coweeta Hydrologic Laboratory, western North Carolina, U.S.A.
- Ca2SiO3OHFA high-pressure phase with dense calcium polyhedral packing and tetrahedral silicon
- Relationships between SEM-cathodoluminescence response and trace-element composition of hydrothermal vein quartz
- Quantitative evaluation of attenuation contrast of X-ray computed tomography images using monochromatized beams
- Biotic and abiotic products of Mn(II) oxidation by spores of the marine Bacillus sp. strain SG-1
- The Mn, Mg-intracrystalline exchange reaction in donpeacorite (Mn0.54Ca0.03Mg1.43Si2O6) and its relation to the fractionation behavior of Mn in Fe, Mg-orthopyroxene
- Crystal structures of chalcostibite (CuSbS2) and emplectite (CuBiS2): Structural relationship of stereochemical activity between chalcostibite and emplectite
- Hydration and swelling of synthetic Na-saponites: Influence of layer charge
- Dehydroxylation and CO2 incorporation in annealed mica (sericite): An infrared spectroscopic study
- Relict coesite exsolution in omphacite from Western Tianshan eclogites, China
- Hyperfine electric field gradients and local distortion environments of octahedrally coordinated Fe2+
- A synchrotron Mössbauer spectroscopy study of (Mg,Fe)SiO3 perovskite up to 120 GPa
- Temporal stability and pressure calibration of barium carbonate and talc/pyrex pressure media in a piston-cylinder apparatus
- Cation ordering in magnesioferrite, MgFe2O4, to 982 °C using in situ synchrotron X-ray powder diffraction
- Halite-sylvite thermoconsolution
- The role of water in the structures of synthetic hallimondite, Pb2[(UO2)(AsO4)2](H2O)n and synthetic parsonsite, Pb2[(UO2)(PO4)2](H2O)n, 0 ≤ n ≤ 0.5
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- Letter. The effect of zinc sulfide on phase transformations of ferrihydrite
- Letter. Stability and equation of state of MgGeO3 post-perovskite phase
- Letter. Pressure dependence of the OH-stretching mode in F-rich natural topaz and topaz-OH
