Chemistry:Tacharanite

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Short description: Calcium aluminium silicate hydrate mineral
Tachanarite
Tachanarite
Globular, white tacharanite (diameter 2.5 mm) from Palagonia, Italy
General
CategoryMineral
Formula
(repeating unit)		Ca
12Al
2Si
18O
33(OH)
36
Strunz classification9.HA.75
Dana classification72.3.2.6
Crystal systemMonoclinic
Space groupA-centered
Unit cella = 17.07 Å,
b = 3.65 Å,
c = 27.9 Å
β = 114.1°
Z = 1
V = 1,586.80 Å3
Identification
Formula mass2,180.68 g/mol[1]
ColorMilky white
Crystal habitCryptocrystalline
CleavagePerfect {001}
FractureConchoidal
TenacityTough
Mohs scale hardness5
|re|er}}Vitreous, earthy, dull
StreakWhite
DiaphaneityTranslucent
Specific gravity2.33 – 2.36
Density2.33 – 2.36 g/cm3
Calculated: 2.28 g/cm3
Optical propertiesBiaxial
Refractive indexnα = 1.518 – 1.525 nγ = 1.530 – 1.537
Birefringence0.0120
DispersionRelatively strong
FusibilityDecompose
Common impuritiesFe, Mg, Na, K
Other characteristicsNon radioactive
References[1][2][3]

Tacharanite is a calcium aluminium silicate hydrate (C-A-S-H) mineral of general chemical formula Ca
12Al
2Si
18O
33(OH)
36 with some resemblance to the calcium silicate hydrate (C-S-H) mineral tobermorite. It is often found in mineral assemblage with zeolites and other hydrated calcium silicates.

C-S-H and C-A-S-H mineral phases are important hydration products of cements but can also be found, although much less frequently, in natural conditions in particular geological environments. The natural specimens are rare and of small size (often available only in limited quantity) but often well crystallised while the hydrated cement phases are disordered and cryptocrystalline or amorphous with a poorly defined stoichiometry denoted by the use of dashes in the abbreviations C-S-H and C-A-S-H.

Etymology

Tachanarite (pronunciation as tă·kherenait: /tɑːkɑːrɑːnaɪt/) was named by Sweet et al. (1961) from the Gaelic word "tacharan", a changeling, "an object or a thing left in place of a thing stolen" alluding to the initially presumed instability of this mineral because after the first X-rays photographic examination it was thought to be unstable when exposed to air and prone to decompose into tobermorite and gyrolite.[5] The name tachanarite was inspired both by the nature of the supposed mineral behaviour and the wealth of folklore associated with the Isle of Skye where it was found.[5]

Stability of the crystal structure

According to Sweet et al. (1961)[5] and Cliff et al. (1975),[6] tacharanite shows some close resemblances to tobermorite, a calcium silicate hydrate (C-S-H) mineral but also significantly differs from it because it contains aluminium in its crystal lattice, making it a member of the calcium aluminium silicate hydrates (C-A-S-H) family. Tacharanite has a monoclinic crystal structure.

Cliff et al. (1975)[6] have also studied the stability of tacharanite standing in air but could not evidence any change. The results of their study thus contradict these of the very first work of Sweet et al. (1961) reporting the change of tacharanite into a mixture of tobermorite and gyrolite which was the main source of inspiration for the mineral name.

A possible explanation for this discrepancy could reside in the impure nature and the quite limited quantity of the mineral samples that Sweet et al. (1961) have studied: they only worked onto a few milligrams (29 mg) of a complex mixture of several minerals very difficult to separate (amongst others, tacharanite, tobermorite and gyrolite...) and nested in the vesicles of the olivine-dolerite intrusive rock.

In 2007, on the basis of a larger number of tacharanite samples, a team of mineralogists from the Russian Academy of Sciences at Moscow (Organova et al., 2007) have comprehensively revisited the crystal structure of this poorly studied mineral.[7] From the tobermorite structure, they derived a model of the tacharanite structure and also established a relationship with a possible zeolite-like structure. Based on these information, they proposed a tentative mechanism of formation considering the overall close presence of zeolite in the systems where tacharanite is found.

Chemical composition

The general chemical composition of tacharanite is most often reported as Ca
12Al
2Si
18O
33(OH)
36.[2][1] Cliff et al. (1975)[6] mention an equivalent composition of Ca
12Al
2Si
18O
69H
36, simply written without expliciting the OH groups.

However, the tacharanite composition is sometimes referred as Ca
12Al
2Si
18O
51 · 18H
2O,[3] or as Ca
12Al
2[Si
6O
17]
3 · 18H
2O,[8] an equivalent notation more explicit for the silicate structure.

Finally, an enigmatic, and less hydrated composition, of Ca
12Al
2Si
18O
15(OH)
2 · 3H
2O[9] is mentioned in the case of a synthesis report on the Maqarin natural analogue.

There is no uncertainties on the content in calcium, aluminium and silicon whose relative ratios are always the same: Ca
12Al
2Si
18. However, the number of oxygen atoms or OH groups present in the hydrate chemical formula can vary, depending on the literature source, and is thus more uncertain, perhaps legitimating the tacharan roots of the name. This aspect needs to be verified before performing geochemical modeling calculations.

Natural occurrences

Spherical, cream-coloured tacharanite on white Na-phillipsite (a mineral series of the zeolite group) from Palagonia, northern Iblean plateau, Sicily, Italy (field of view 1 cm).

Tacharanite was first identified by Sweet et al. (1961) in vesicles of an intrusive igneous rock injected into a vein in the parent rock) at a small outcrop at Portree, Trotternish, Isle of Skye, Inner Hebrides islands, Highland of Scotland, UK. Tacharanite is associated there with other hydrated calcium silicates (tobermorite, gyrolite and xonotlite) and zeolites (aluminosilicates: laumontite, mesolite, thomsonite, and analcime) also found in neighbouring localities.[5] It was first presumed by Sweet et al. (1961) to be a new member of the tobermorite group.[5]

In 1961, tacharanite was also identified in Tasmania (Australia) by Sutherland who made a second parallel discovery of the mineral quasi at the same time as Sweet et al. (1961), but published his results later.[10]

Tacharanite natural occurrence has also been considered in the frame of the characterization works and geochemical modelling of the natural analogue sites of Khushaym Matruk and Maqarin in central and northern Jordan where natural alkaline plumes are driven in the rock formation by the diffusion of very basic fluids with a high pH.[9]

Tacharanite is also present in the clastic dikes of the Hatrurim basin (western flank of the Dead Sea) studied as natural analogues of alkaline concrete.[11]

Natural analogue studies inspired by the first works on natural calcium silicate hydrates, closely related to the chemistry of cement,[12] are performed to better understand the behaviour of an alkaline perturbation developing around the galleries of a cementitious radioactive waste repository.

Cement hydration products

C-S-H (the "cement glue") and C-A-S-H phases are essential phases of the hardened cement paste (HCP) contributing to the development of the concrete strength. They are formed by the hydration of the cement clinker and ground granulated blast-furnace slags (GGBFS). Harry F. W. Taylor, eminent cement chemist at the University of Aberdeen (Scotland, UK), was a pioneer and an indefatigable artisan in their detailed characterisation.[13][14][15][12] This explains the interest of Taylor, Cliff, and their colleagues[6] for reappraising in 1975 the crystal structure and the stability of tachanarite, a decade after the two parallel discoveries in 1961 of the mineral by Sweet et al.[5] at Portree (Isle of Skye, Scotland) and Sutherland[10] in Tasmania.

Cement–clay interactions

Tacharanite has received additional attention in the context of natural analogue studies undertaken to investigate the possible effects of an alkaline plume developing around a high-level radioactive waste repository.[16]

In the frame of the geological disposal of high-level radioactive waste and spent fuel, large amounts of concrete will be used in the near-field of a deep geologic repository. Cementitious materials will serve as waste immobilization matrix, buffer materials, backfill materials, and also for the lining of galleries (shotcrete and concrete blocks). The high pH prevailing in concrete pore water is beneficial for immobilizing radionuclides (low solubility, high sorption and limitation of the microbial activity). Since the mid-1980, many studies were initiated after the pioneering works of Atkinson et al. (1985, 1988, 1990) at UKAEA (Harwell) to assess the time dependence of pH in a radioactive waste repository.[17][18][19] Simultaneously, also emerged the question of the geochemical perturbation induced by an alkaline plume developing in an argillaceous environment. Indeed, the integrity of the repository near field could be compromised as large quantities of concrete will be placed in direct contact with the host rock (clay sedimentary formation or granite). The pore water of the hardened cement paste (HCP) of concrete is hyperalkaline with a high pH. When Portland cement is used, young cement water (YCW) rich in potassium hydroxide (KOH) and sodium hydroxide (NaOH) has initially a very high pH of ~ 13.5. Latter in the cement degradation stages, evolved cement water (ECW) has a pH of 12.5 controlled by the dissolution of portlandite (Ca(OH)2). The hydroxide anions (OH−
) released by the concrete in contact with clay pore water, or granite groundwater, slowly diffuse into the host geological formation where they interact with the various mineral phases of the surrounding rock. Inside a backfilled gallery, and in the seals of drifts and shafts the same process will also affect the clay minerals of the bentonite buffer material. Water-rock interactions lead to complex dissolution and precipitation reactions at the interface between cement and clay materials. The main reaction products of an alkaline plume in clay are calcium silicate hydrates (C-S-H) and zeolites potentially contributing to clogging the porosity at the cement-clay interface.

As tacharanite is a member of the family of the calcium aluminium silicate hydrates (C-A-S-H), it has also been identified as a potentially newly formed minerals in the frame of the cement–clay interactions and taken into account for the geochemical modelling studies.[20][21]

See also

References

  1. ↑ 1.0 1.1 1.2 Barthelmy, Dave. "Tacharanite Mineral Data" (in En). webmineral.com. http://webmineral.com/data/Tacharanite.shtml#. 
  2. ↑ 2.0 2.1 Mindat. "Tacharanite" (in En). mindat.org. https://www.mindat.org/min-3864.html. 
  3. ↑ 3.0 3.1 Handbook of Mineralogy (2001). "Tacharanite" (in En). handbookofmineralogy.org. http://www.handbookofmineralogy.org/pdfs/tacharanite.pdf. 
  4. ↑ Warr, Laurence N. (18 May 2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine 85 (3): 291–320. doi:10.1180/mgm.2021.43. ISSN 0026-461X. Bibcode: 2021MinM...85..291W. 
  5. ↑ 5.0 5.1 5.2 5.3 5.4 5.5 Sweet, Jessie M.; Bothwell, D. I.; Williams, D. L. (June 1961). "Tacharanite and other hydrated calcium silicates from Portree, Isle of Skye". Mineralogical Magazine and Journal of the Mineralogical Society 32 (253): 745–753. doi:10.1180/minmag.1961.032.253.01. ISSN 0369-0148. Bibcode: 1961MinM...32..745S. 
  6. ↑ 6.0 6.1 6.2 6.3 Cliff, G.; Gard, J. A.; Lorimer, G. W.; Taylor, H. F. W. (June 1975). "Tacharanite". Mineralogical Magazine 40 (310): 113–126. doi:10.1180/minmag.1975.040.310.01. ISSN 0026-461X. Bibcode: 1975ClMin..40..113C. 
  7. ↑ Organova, N. I.; Zadov, A. E.; Chukanov, N. V.; Dubinchuk, V. T.; Kuznetsova, O. Yu.; Trubkin, N. V.; Levitskaya, L. A.; Marsii, I. M. (May 2007). "Structural model of the rare mineral tacharanite and a possible process of its formation". Bulletin of the Russian Academy of Sciences: Physics 71 (5): 635–637. doi:10.3103/S1062873807050115. ISSN 1062-8738. Bibcode: 2007BRASP..71..635O. 
  8. ↑ Stefan Weiß (2008). Das große lapis mineralienverzeichnis. Alle mineralien von A – Z und ihre eigenschaften (5. Completely revised and supplemented ed.). München, Germany: Weise. ISBN 978-3-921656-70-9. 
  9. ↑ 9.0 9.1 A natural analogue study of cement buffered, hyperalkaline groundwaters and their interaction with a repository host rock IV: an examination of the Khushaym Matruk (central Jordan) and Maqarin (northern Jordan) sites. An international project jointly funded by NDA-RWMD, ANDRA, CEA, JAEA, Nagra and SKB. Bedrock Geosciences Technical Report 11-02 (BG-TR-11-02) (Report). 2011. https://www.researchgate.net/publication/275946228. 
  10. ↑ 10.0 10.1 Sutherland, F. L. (December 1976). "Tacharanite from Tasmania, Australia". Mineralogical Magazine 40 (316): 887–890. doi:10.1180/minmag.1976.040.316.10. ISSN 0026-461X. Bibcode: 1976MinM...40..887S. 
  11. ↑ Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N. (November 2014). "Clastic dikes of the Hatrurim basin (western flank of the Dead Sea) as natural analogues of alkaline concretes: Mineralogy, solution chemistry, and durability". Doklady Earth Sciences 459 (1): 1436–1441. doi:10.1134/S1028334X14100122. ISSN 1028-334X. Bibcode: 2014DokES.459.1436S. https://www.researchgate.net/publication/278398576. 
  12. ↑ 12.0 12.1 Taylor, Harry F. W. (1997). Cement Chemistry. Thomas Telford. ISBN 978-0-7277-2592-9. https://books.google.com/books?id=1BOETtwi7mMC. 
  13. ↑ Taylor, Harry F. W. (1959). "The chemistry of cement hydration". Progress in Ceramic Science 1: 89–145. 
  14. ↑ Taylor, Harry F. W. (1960). "Aspects of the crystal structures of calcium silicates and aluminates". Journal of Applied Chemistry 10 (8): 317–323. doi:10.1002/jctb.5010100802. ISSN 0021-8871. 
  15. ↑ Taylor, Harry F.W. (1986). "Proposed structure for calcium silicate hydrate gel". Journal of the American Ceramic Society 69 (6): 464–467. doi:10.1111/j.1151-2916.1986.tb07446.x. ISSN 0002-7820. 
  16. ↑ A natural analogue study of cement buffered, hyperalkaline groundwaters and their interaction with a repository host rock: Phase II. Nirex Science Report, S-98-003, UK Nirex, Harwell, U.K. (Report). 1998. 
  17. ↑ Atkinson, Alan (1985) (in English). The time dependence of pH within a repository for radioactive waste disposal. AERE R11777 (Report). Harwell: UK Atomic Energy Agency, UKAEA. 
  18. ↑ Atkinson, Alan; Everitt, Nicoia M.; Guppy, Richard M. (1988). "Time dependence of pH in a cementitious repository" (in English). MRS Proceedings 127. doi:10.1557/PROC-127-439. ISSN 0272-9172. 
  19. ↑ Atkinson, A.; Hearne, J. A.; Knights, C. F. (1990). "Thermodynamic modelling and aqueous chemistry in the CaO-Al2O3-SiO2-H2O system". MRS Proceedings 212. doi:10.1557/PROC-212-395. ISSN 0272-9172. 
  20. ↑ Gaucher, Eric C.; Blanc, Philippe (January 2006). "Cement/clay interactions – A review: Experiments, natural analogues, and modeling". Waste Management 26 (7): 776–788. doi:10.1016/j.wasman.2006.01.027. ISSN 0956-053X. PMID 16574392. Bibcode: 2006WaMan..26..776G. https://hal-brgm.archives-ouvertes.fr/hal-00664858/document. 
  21. ↑ Savage, David; Walker, Colin; Arthur, Randy; Rochelle, Chris; Oda, Chie; Takase, Hiro (January 2007). "Alteration of bentonite by hyperalkaline fluids: A review of the role of secondary minerals". Physics and Chemistry of the Earth, Parts A/B/C 32 (1–7): 287–297. doi:10.1016/j.pce.2005.08.048. ISSN 1474-7065. Bibcode: 2007PCE....32..287S. 

Further reading

  • McConnell, J. D. C. (March 1954). "The hydrated calcium silicates riversideite, tobermorite, and plombierite". Mineralogical Magazine and Journal of the Mineralogical Society 30 (224): 293–305. doi:10.1180/minmag.1954.030.224.02. ISSN 0369-0148. Bibcode: 1954MinM...30..293M. 
  • Hodgkinson, Emily, Sarah (1998). The mineralogy and geochemistry of cement/rock interactions – PhD thesis (Proquest number 10729393) (Thesis). The University of Manchester (United Kingdom). Retrieved 2022-12-26.
  • Hodgkinson, Emily S.; Hughes, Colin R. (January 1999). "The mineralogy and geochemistry of cement/rock reactions: high-resolution studies of experimental and analogue materials". Geological Society, London, Special Publications 157 (1): 195–211. doi:10.1144/GSL.SP.1999.157.01.15. ISSN 0305-8719. Bibcode: 1999GSLSP.157..195H. 
  • Savage, David; Noy, David; Mihara, Morihiro (March 2002). "Modelling the interaction of bentonite with hyperalkaline fluids". Applied Geochemistry 17 (3): 207–223. doi:10.1016/S0883-2927(01)00078-6. ISSN 0883-2927. Bibcode: 2002ApGC...17..207S. 

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