The Crystal Structure of Franzinite, the Ten-Layer Mineral of the Cancrinite Group

Ballirano, Paolo; Bonaccorsi, Elena; Maras, Adriana; Merlino, Stefano

doi:10.2113/gscanmin.38.3.657

Cited by 41 publications

(33 citation statements)

References 8 publications

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“…These values show, apart from an <Al-O> distance slightly larger, a smaller distortion than those reported by Ballirano et al (1997). The <Si-O>/<Al-O> ratio has a value of 0.931 identical to that observed in liottite (Ballirano et al 1996b) and slightly smaller than 0.936 reported in the previous afghanite-structure refinement (Ballirano et al 1997). The framework consists of columns of cancrinite or ε cages ([4 6 6 5 ] polyhedra following the IUPAC nomenclature, McCusker et al 2001) stacked along the threefold axis located at 0, 0, z, and regularly alternating liottite ([4 6 6 17 ] polyhedra) and cancrinite cages piled along the threefold axes located at 2/3, 1/3, z and 1/3, 2/3, z.…”

Section: Frameworksupporting

confidence: 57%

“…4). Such coupled Cl → F substitution and Ca atoms shift also occurs in liottite (Ballirano et al 1996b). The Cl thermal ellipsoids have been reported to be consistently flattened in both structure and this has been interpreted in terms of a small off-axis displacement of the Cl atoms that was found impossible to model using a static disorder.…”

Section: Cancrinite Cagesmentioning

confidence: 78%

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Thermal behavior of afghanite, an ABABACAC member of the cancrinite group

Ballirano

Bosi

2012

American Mineralogist

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Thermal behavior of afghanite, (Na15K5Ca11)Sigma(31)[Si24Al24O96](SO4)(6)Cl-6, P31c, a = 12.7961(7) angstrom, c = 21.4094(13) angstrom, an eight-layer member of the cancrinite group, has been investigated by combined electron microprobe analysis, X-ray single-crystal diffraction, and high-temperature X-ray powder diffraction. Non-ambient X-ray powder diffraction data were collected in the 323-1223 K thermal range on a specimen from Case Collina, Latium, Italy. Structural refinement and site assignment based on the bond-valence analysis, performed on room-temperature single-crystal X-ray diffraction data, provided more accurate site allocation of cations than the available model in the literature. The results show that the cancrinite cages alternating with the liottite cages are more compressed along the c-axis than the remaining ones. As a result the chlorine atom, located at the center of the cages, is driven off-axis to release the steric strain due to the cage compression. Thermal expansion shows a discontinuity at 448 K for both a and c unit-cell parameters, a feature previously reported for other cancrinite-like minerals. Up to 448 K, the c-parameter expands significantly and more than the aparameter. A further discontinuity has been detected at 1073 K for the c-parameter. Mean linear and volume thermal expansion coefficients (x10(-6) K-1) in the 323 < T< 448 K thermal range are (alpha) over bar (a), = 12.9(4), (alpha) over bar (c) = 17.9(9), and (alpha) over bar (v) = 43.7(18). Above this discontinuity temperature, the thermal expansion is reverted becoming greater for the a-parameter. Mean linear and volume thermal expansion coefficients in the 448 < T < 1073 K thermal range are (alpha) over bar (c) = 8.22(3), (alpha) over bar (c) = 3.52(4), and (alpha) over bar (v) = 19.68(8). In the 1073 < T < 1223 K thermal range the values are (alpha) over bar (a) = 6.35(9), (alpha) over bar (c) = 5.02(14), and (alpha) over bar (v) = 17.74(9). Afghanite shows a significant microstrain at RT that increases up to ca. 700 K and subsequently decreases as a function of T. Cooling to RT allows a significantly release of epsilon(0) microstrain, which is coupled with a significant expansion of the c-parameter as compared to the starting RT data. The expansion of the c-parameter has been mainly attributed to the full expansion of the cancrinite cages alternating with the liottite cages. Upon reheating at 1173 K, the microstrain increases back to approximately the same value calculated for the first heating process. Repeated heating-RT-cooling cycles led to the partial afghanite structure disruption and the partial conversion, via an intermediate disordered phase, to hatiyne. As repeated heating/cooling cycles did not modify the epsilon(0) values both at RT and at HT, it can therefore be concluded that the strain release occurs prevalently during the first heating/cooling cycle

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Section: Frameworksupporting

confidence: 57%

Section: Cancrinite Cagesmentioning

confidence: 78%

Thermal behavior of afghanite, an ABABACAC member of the cancrinite group

Ballirano

Bosi

2012

American Mineralogist

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“…Both sodalite and cancrinite are called "reservoir minerals" because of their large cation-exchange capacities (Buhl and Lons 1996). In addition to providing the mineral with a higher specific surface area, the cages host a complex distribution of extra-frame-work cations and anions (Ballirano et al 2000). Morphological features of the neophases were found to change with the aqueous silicon/aluminum ratio.…”

Section: 7mentioning

confidence: 99%

Remediation of Uranium in the Hanford Vadose Zone Using Ammonia Gas: FY 2010 Laboratory-Scale Experiments

Szecsody¹,

Truex²,

Zhong³

et al. 2010

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Executive SummaryThis investigation is focused on refining an in situ technology for vadose zone remediation of uranium by the addition of ammonia (NH 3 ) gas with no addition of water. The objectives were to: a) refine the technique of ammonia gas treatment, b) identify the geochemical changes in uranium surface phases, c) identify broader geochemical changes that occur, and d) predict and test injection of ammonia gas for intermediate-scale systems to identify process interactions that could impact field-scale implementation. For ammonia gas injection into vadose zone sediments to be successful as a uranium remediation technology, it needs to show decreased U mobility of the most mobile U phases (aqueous, adsorbed) in a variety of field conditions. Uranium is present in Hanford sediment include in multiple phases including aqueous U(VI)-carbonate complexes, adsorbed, uranium coprecipitated with carbonates, and U-bearing minerals Na-boltwoodite and uranophane. Ammonia treatment of sediments raises the pH in Hanford sediments from 8.0 to 11-13, which has resulted in a decrease in uranium mobility, as evidenced by decrease in aqueous and adsorbed uranium in 85% of the different sediments tested (different U surface phase distributions or NH 3 treatments) and an increase in 8M HNO 3 extracted U (hard to extract U phases, silicates/phosphates/oxides) for 79% of sediments tested. There were also inconsistent changes in two acetate extractions, likely the result of dissolution of multiple surface U phases (U-carbonates, Na-boltwoodite, uranophane). Surface phase analysis by laser induced fluorescence spectroscopy and extended x-ray absorption structure has showed essentially no U surface mineral change in sediments initially containing Na-boltwoodite, but some U surface phase changes in U-calcite coprecipitates to uranyl oxyhydroxide, Na-boltwoodite, and uranyl tricarbonate. Therefore, the ammonia gas treatment appears most effective for U present in the most mobile phases: aqueous U, adsorbed U, and carbonate associated U. NH 3 -treated sediments containing Na-boltwoodite and uranophane showed decreased leaching even though solid phase analysis showed little changes in the U mineralogy. The decreased leaching may be the result of other mineral precipitates coating these phases. Minerals that leached the most significant mass of ions were montmorillonite, muscovite, and kaolinite. A greater understanding of these dissolution/precipitation/coating processes is needed to predict the long-term impact on uranium mobility.Ammonia gas injection experiments conducted in 20-to 30-ft long 1-D systems and a layered 2-D radial flow system were used to characterize the physicochemical changes at the NH 3 reaction front and treatment coverage in heterogeneous sediments. For 5% NH 3 (95%N 2 ) injection, an average of 234 pore volumes were needed to achieve the elevated pH (10.2 to 11.4) of the reaction front observed, with 465 pore volumes needed to achieve pH equilibrium (pH = 11.88), at 4% water content and 35% porosity. The des...

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“…, 4 los, 12 sod,Pobedimskaya et al 1991; (2)Ballirano et al 1996b; (3)Ballirano et al 1997;(4)Ballirano et al 2000; (5) Rozenberg et al 2004; (6) Bonaccorsi and Orlandi 2004; (7) Camara et al 2004; (8) Bonaccorsi 2004; (9) Ballirano 1994; (10) Ballirano and Bonaccorsi (pers. commun.)…”

mentioning

confidence: 99%

Modular Microporous Minerals: Cancrinite-Davyne Group and C-S-H Phases

Bonaccorsi

2005

Reviews in Mineralogy and Geochemistry

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In this chapter, we illustrate and discuss two distinct groups of microporous phases: the cancrinite group and the C-S-H compounds of the tobermorite and gyrolite families. The compounds in the fi rst group present a three-dimensional purely tetrahedral framework with, apart from a single exception, Si:Al ratio equal to 1; in the mineralogical classifi cations they are included among feldspathoids and are generally “regarded …… distinct from zeolites, in part, at least, because of the presence of large volatile anions” (Coombs et al. 1998). The members of the second group are characterized by mixed frameworks built up by silicon (and aluminum) tetrahedra and calcium polyhedra. A common feature of both groups is the modular character of their frameworks, which are built up through various stacking ways of a single module (as in the minerals of the cancrinite-davyne family) and two or more modules as in the case of the C-S-H phases

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The Crystal Structure of Franzinite, the Ten-Layer Mineral of the Cancrinite Group

Cited by 41 publications

References 8 publications

Thermal behavior of afghanite, an ABABACAC member of the cancrinite group

Thermal behavior of afghanite, an ABABACAC member of the cancrinite group

Remediation of Uranium in the Hanford Vadose Zone Using Ammonia Gas: FY 2010 Laboratory-Scale Experiments

Modular Microporous Minerals: Cancrinite-Davyne Group and C-S-H Phases

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