Clinoptilolite series | Clinoptilolite-K |(K,Na,Ca0.5,Sr0.5,Ba0.5,Mg0.5)6(H2O)20|[Al6 Si30 O72] |
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Morphology: | |||
Monoclinic 2/m, platy crystals with prominent {010} face, modified by and {001}, {100}, {111}, {201} and {110}. | |||
Physical properties: | |||
Cleavage: {010} perfect. |
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Clinoptilolite-Ca with smectite on surface of rhyolite ignimbrite, Richardson’s Ranch north of Madras, Jefferson County, Oregon, USA. Width of view 5 mm. | |||
Optical properties: | |||
Color: | Colorless, white, yellowish, pinkish, orange to red; colorless in thin section | ||
Clinoptilolite-Na partial pseudomorph of glass shard (0.25 mm in length) from the Miocene, Barstow formation, San Bernardino County, California, USA. Crossed polars. Image courtesy of R. A. Sheppard (see Sheppard and Gude 1969). | |||
Biaxial (+ or -), |
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Clinoptilolite-K: | α 1.476 - 1.478, β 1.477 - 1.479 , γ 1.479 - 1.481 , δ 0.003,
2Vz 58 - 73°, Y = b, Z ˄ c 38° - 58°
(or Z = b). |
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Clinoptilolite-Na: | α 1.474 - 1.478, β 1.475 - 1.479, γ 1.478 - 1.481, δ 0.003 – 0.004, |
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Clinoptilolite-Ca: | α 1.481, β 1.484, γ 1.488, δ 0.007,
2Vz 70°, Z = b, X ˄ c 20°. |
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Crystallography: | |||
Unit cells: | |||
Clinoptilolite-K | a 17.688(16), b 17.902(9), c 7.409 (7) Å, β 116.50(7)°. |
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Clinoptilolite-Na | a 17.627(4), b 17.955(4), c 7.399(4) Å, β 116.29(2)°. |
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Clinoptilolite-Ca | a 17.660(4), b 17.963(5), c 7.400(3) Å, β 116.47(3)°. |
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Names: | |||
The origin and use of the name clinoptilolite has a convoluted history. The type locality is Mason and Sand (1960) proposed a new definition for clinoptilolite, based on alkali-dominant and high Si/Al compositions. Mumpton (1960) simultaneously suggested that the name be applied to those samples that remained stable following overnight heating to 350°C. This method works particularly well for the fined-grained replacements of vitric tuff. During the following years the compositional gap observed by Mason and Sand (1960) was filled by the analysis of many newly discovered samples. Even so, the subcommittee reviewing the nomenclature of the zeolite group (Coombs et al. 1997) chose to retain the two mineral names, and proposed to keep both the heulandite and clinoptilolite names and to separate them based on the framework composition at Si/Al = 4.0. For a discussion of this nomenclature problem and some guidance in distinguishing between heulandite and clinoptilolite, see Bish and Boak (2001). Both names were also raised to series status to include several species based on the dominant cation content. The clinoptilolite series comprises three species. Clinoptilolite-K is the new name for the original material from the ridge east of Hoodoo Peak, Wyoming. Clinoptilolite-Nais a new name for Na dominant crystals with the suggested type example from the Barstow formation, San Bernardino County, California, USA, and clinoptilolite-Cafor Ca dominant samples with type examples from Kuruma Pass, Fukushima Prefecture, Japan. |
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Crystal structure: | |||
Both clinoptilolite and heulandite possess the same tetrahedral framework (labeled HEU) and form a continuous compositional series sometimes referred to as the heulandite group zeolites. The crystal structures of clinoptilolite and heulandite are mostly described to be monoclinic, space group C2/m (e.g. Alberti 1975, Koyama and Takéuchi 1977, Bresciani-Pahor et al. 1980, Alberti and Vezzalini 1983, Hambley and Taylor 1984, Smyth et al. 1990, Armbruster and Gunter 1991, Armbruster 1993, Gunter et al. 1994, Cappelletti et al. 1999). However, lower symmetries such as Cm and C1 have also been reported (Alberti 1972, Merkle and Salughter 1968, Gunter et al. 1994, Yang and Armbruster 1996, Sani et al. 1999, Stolz et al. 2000a). The HEU framework contains three sets of intersecting channels all located in the (010) plane. Two of the channels are parallel to the c-axis: the A channels are formed by strongly compressed ten-membered rings (aperture 3.0 x 7.6 Å) and B channels are confined by eight-membered rings (aperture 3.3 x 4.6 Å). C channels are parallel to the a-axis, or [102] and are also formed by eight-membered rings (aperture 2.6 x 4.7 Å). Alberti (1972) concluded that the true probable lower symmetry of heulandite cannot reliably be extracted from X-ray single crystal data because of strong correlations of C2/m pseudo-symmetry related sites during the least-squares procedure. Thus C1, C1, Cm, C2, C2/m are possible space groups for clinoptilolite and heulandite. Akizuki et al. (1999) determined by optical methods and X-ray diffraction that a macroscopic heulandite crystal is composed of growth sectors displaying triclinic and monoclinic symmetry where the triclinic sectors are explained by (Si,Al) ordering on the crystal faces. Yang and Armbruster (1996) and Stolz et al. (2000a,b) stated that, owing to correlation problems, symmetry lowering in heulandite can only be resolved from X-ray data when investigated in cation-exchanged samples where the distribution of non-framework cations also reflects the lower symmetry. Differing degrees of (Si,Al) ordering over the five distinct tetrahedral sites (assuming C2/m space group) have been reported for both heulandite and clinoptilolite. In all refinements, the tetrahedron with the highest Al content, T2, joins the “sheets” of T10O20 groups by sharing their
apical oxygens. A neutron diffraction study by Hambley and Taylor (1984) located the majority of the H atoms and found (Si,Al) ordering values similar to other C2/m refinements. Additional (Si,Al) ordering, due to lower symmetry (C1 or Cm), was resolved by Yang and Armbruster (1996), Sani et al. 1999, and Stolz et al. (2000a,b). Clinoptilolite and heulandite contain differing amounts of H2O as a function of their non-framework cation chemistry (Bish 1988, Yang and Armbruster 1996) and hydration state. The H2O molecules occurring in the B channel (coordinated to Ca) are commonly fully occupied, whereas those occurring in the A channel are generally only partially occupied (Koyama and Takéuchi 1977, Armbruster and Gunter 1991). The structural mechanism of dehydration and accompanying framework distortion were studied by Alberti (1973), Alberti and Vezzalini (1983), Armbruster and Gunter (1991), and Armbruster (1993). |
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The crystal structure of clinoptilolite-Na (Agoura, California) with cation positions from the refinement of Koyama and Takéuchi (1977). Typically clinoptilolite contains 4 to 7 cations per unit cell (Deer et al. 2004).
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Chemical composition: |
Representative analyses of the three clinoptilolite species are plotted in the figures below. These species occur as diagenetic alteration products of volcaniclastic sediment in saline lakes and marine accumulations, including pelagic and siliceous clays in deep sea sediments, and in cavities in volcanic rocks ranging in composition from basalt to rhyolite. By the new definitions (Coombs et al. 1997) these species have high Si contents, Si/Al greater than 4.0, and TSi greater than 0.80. Clinoptilolite-K is the most widespread, mostly because deep sea clinoptilolite is K-dominant. However, there are also many occurrences in rhyolitic tuffs from terrestrial and marine environments. Both clinoptilolite-Na and clinoptilolite-Ca occur in a wide range of environments, including diagenetic replacement of rhyolitic volcaniclastic rocks, active hydrothermal systems, and fractures and cavities in volcanic rocks. Mg occurs in almost all clinoptilolite, but high amounts (greater than 1 weight %) may reflect included smectitic clay in those from volcaniclastic rocks. As in other zeolites, Fe is most likely Fe3+ and resides in tetrahedral sites, but amounts over 0.5 atoms/cell may be from included hematite. Sr and Ba are much less common in clinoptilolite species than heulandite. Nonetheless, Mg, Sr, and Ba should always be sought when analyzing a member of the heulandite structural group. |