Palygorskite

Palygorskite
A sample of palygorskite from Hnúšťa, Slovakia.
General
Category	Phyllosilicate[1][2]
Formula (repeating unit)	(Mg,Al)2Si4O10(OH)·4(H2O) Al2Mg2◻2Si8O20(OH)2(H2O)4 · 4H2O[3]
IMA symbol	Plg[4]
Strunz classification	9.EE.20[3]
Crystal system	Monoclinic,[3] orthorhombic[5]
Crystal class	Prismatic (2/m)[3] (same H-M symbol)
Space group	B2/m and setting C2/m, [3] P 21 21 21[6]
Unit cell	a = 12.78 Å, b = 17.86 Å, c = 5.24 Å; β = 95.78°; Z = 4[3]
Identification
Color	White, grayish, yellowish, gray-green[3]
Crystal habit	Commonly fibrous, tangled mats known as mountain leather. Individual, small crystals are lath-shaped[3]
Cleavage	Distinct/good, good on {110}[3]
Tenacity	Tough[3]
Mohs scale hardness	2 – 2.5[3]
Luster	Waxy, earthy[3]
Diaphaneity	Translucent[3]
Specific gravity	1 – 2.6[3]
Density	2.1 - 2.6 g/cm3 (Measured); 2.35 g/cm3 (Calculated)[3]
Optical properties	Biaxial (−)[3]
Refractive index	nα = 1.522 – 1.528 nβ = 1.530 – 1.546 nγ = 1.533 – 1.548[3]
Birefringence	δ = 0.011 – 0.020[3]
Pleochroism	X= pale yellow Y=Z= pale yellow-green[3]
Common impurities	Fe,K [3]
References	[1][2][3][7]

Palygorskite (Russian: Палыгорскит) or attapulgite is a magnesium aluminium phyllosilicate with the chemical formula (Mg,Al)₂Si₄O₁₀(OH)·4(H₂O) that occurs in a type of clay soil common to the Southeastern United States. It is one of the types of fuller's earth. Some smaller deposits of this mineral can be found in Mexico, where its use is tied to the manufacture of Maya blue in pre-Columbian times.^[2][3][8]

Name

Palygorskite was first described in 1862 for a deposit at Palygorskaya on the Popovka River,^[9] Middle Urals, Permskaya Oblast, Russia.^[3][7] The synonym attapulgite is derived from the U.S. town of Attapulgus, in the extreme southwest corner of the state of Georgia, where the mineral is abundant and surface-mined.

Origin

Five processes for the genesis of palygorskite were discussed in the older literature:^[10]

1. Formation under arid conditions,
2. Formation connected with the weathering of basalt,
3. Hydrothermal genesis,
4. Synsedimentary (during sedimentary deposition) authigenesis,
5. Postsedimentary (following sedimentary deposition) formation.

Mining and usage

Mineral deposit in the US

Two companies are involved in the industrial extraction and processing of gellant-grade attapulgite clay within the same Attapulgus deposit: Active Minerals International, LLC, and BASF Corp. In 2008, BASF acquired the assets of Zemex Attapulgite, leaving only two gellant-grade producers. Active Minerals operates a dedicated factory to produce the patented product Actigel 208 and built a new state-of-the-art production process in early 2009 involving portable plant processing at the mine site.^[11]

Properties

Attapulgite clays are a composite of smectite and palygorskite. Smectites are expanding lattice clays, of which bentonite is a commonly known generic name for smectite clays. The palygorskite component is an acicular bristle-like crystalline form that does not swell or expand. Attapulgite forms gel structures in fresh and salt water by establishing a lattice structure of particles connected through hydrogen bonds.

Attapulgite, unlike some bentonite (sodium-rich montmorillonites), can gel in seawater,^[12] forming gel structures in salt water and is used in special saltwater drilling mud for drilling formations contaminated with salt. Palygorskite particles can be considered as charged particles with zones of positive and negative charges. The bonding of these alternating charges allows them to form gel suspensions in salt and fresh water.

Attapulgite clays found in the Meigs-Quincy district are bundles of palygorskite clay particles between 2 and 3 μm long and below 3 nm in diameter. The bundles are surrounded by a matrix of smectite clays that are slightly swellable. Dry-process grades contain up to 25% non-attapulgite material in the form of carbonates and other mineral inclusions. Processing of the clays consist of drying and grinding the crude clay to specific particle size distributions with specific ranges of gel viscosity measured by a variety of means depending on the end use.

Gel-grade, dry-processed attapulgites are used in a very wide range of applications for suspension, reinforcement, and binding properties. Paints, sealants, adhesives, tape-joint compound, catalysts, suspension fertilizers, wild-fire suppressants, foundry coatings, animal feed suspensions, and molecular sieve binders are just a few uses of dry-process attapulgite.

7–10% attapulgite clay mixed with the eutectic salt, sodium sulfate decahydrate (mirabilite or Glauber's salt), keeps anhydrous crystals suspended in the solution, where they hydrate during phase transition and hence contribute to the heat absorbed and released when Glaubers salt is used for heat storage.

Stabilization of nanopalygorskite suspensions was improved using mechanical dispersion (magnetic stirring, high-speed shearing and ultrasonication) and polyelectrolytes (carboxymethyl cellulose, alginate, sodium polyphosphate, and poly(sodium acrylate)) at different pH.^[13] Surface energy and nanoroughness were studied in a palygorskite sample.^[14]

Medical use

Attapulgite is used widely in medicine. Taken by mouth, it physically binds to acids and toxic substances in the stomach and digestive tract. Also, as an antidiarrheal, it was believed to work by adsorbing the diarrheal pathogen. For this reason, it has been used in several antidiarrheal medications, including Diar-Aid, Diarrest, Diasorb, Diatabs, Diatrol, Donnagel, Kaopek, K-Pek, Parepectolin, and Rheaban.^[15] It has been used for decades to treat diarrhea.

Until 2003, Kaopectate marketed in the US also contained attapulgite. However, at that time, the U.S. Food and Drug Administration retroactively rejected medical studies showing its efficacy, calling them insufficient.^[16][17] Kaopectate's U.S. formula was changed to bismuth subsalicylate (pink bismuth). The next year (2004), an additional change in labeling was made; from then on, Kaopectate was no longer recommended for children under 12 years old.^[18] Nevertheless, Kaopectate with attapulgite is still available in Canada and elsewhere. Until the early 1990s, Kaopectate used the similar clay product kaolinite with pectin (hence the name).

Construction

Palygorskite can be added to lime mortar with metakaolin for period-correct restoration of mortar at cultural heritage sites.^[19]

In human culture

Palygorskite is known to have been a key constituent of the pigment called Maya blue, which was used notably by the pre-Columbian Maya civilization of Mesoamerica on ceramics, sculptures, murals, and (most probably) Maya textiles. The clay mineral was also used by the Maya as a curative for certain illnesses, and evidence shows it was also added to pottery temper.

A Maya region source for palygorskite was unknown until the 1960s, when one was found at a cenote on the Yucatán Peninsula near the modern township of Sacalum, Yucatán. A second possible site was more recently (2005) identified, near Ticul, Yucatán.^[20]

The Maya blue synthetic pigment was also manufactured in other Mesoamerican regions and used by other Mesoamerican cultures, such as the Aztecs of central Mexico. The blue coloration seen on Maya and Aztec codices, and early colonial-era manuscripts and maps, is largely produced by the organic-inorganic mixture of añil leaves and palygorskite, with smaller amounts of other mineral additives.^[21] Human sacrificial victims in postclassic Mesoamerica were frequently daubed with this blue pigmentation.^[22]

• 
  Electron diffractogram of palygorskite (Wiersma 1970).
• 
  Electron micrograph of palygorskite (Wiersma 1970).
• 
  Palygorskite variant Pilolite, "mountain leather", with "modulated layers" of growth, feeling like flexible leather, Seaton, Devon, UK, before 2011.
• 
  Rows of colorless calcite crystals held together by layers of papery palygorskite. From Metaline Falls, Washington, USA, 2013.
• 
  Palygorskite. Estonian Museum of Natural History, 2015.

See also

• Sepiolite – Soft and porous white magnesium silicate clay mineral
• Talc – Hydrated magnesium phyllosilicate mineral

Notes

1. "Palygorskite Mineral Data". Webmineral.com. David Barthelmy. 2024. Archived from the original on 2024-04-20. Retrieved 29 August 2024.
2. Lu, Yushen; Wang, Aiqin (2022). "From structure evolution of palygorskite to functional material: A review". Microporous and Mesoporous Materials. 333: 111765. Bibcode:2022MicMM.33311765L. doi:10.1016/j.micromeso.2022.111765. Retrieved 20 September 2009.
3. "Palygorskite. A valid IMA mineral species - grandfathered". Mindat.org. Hudson Institute of Mineralogy. 2024. Retrieved 29 August 2024.
4. Warr, L.N. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine. 85 (3): 291–320. Bibcode:2021MinM...85..291W. doi:10.1180/mgm.2021.43. S2CID 235729616.
5. Garcia-Rivas, Javier; Sánchez del Río, Manuel; García-Romero, Emilia; Suárez, Mercedes 2017
6. Wiersma 1970, p. 87.
7. "Palygorskite (Mg,Al)₂ Si₄ O₁₀ (OH).4H2O" (PDF). handbookofmineralogy.com. Mineral Data Publishing, version 1.2. 2001. Archived from the original (PDF) on 2022-05-01. Retrieved 29 August 2024. Palygorskite in the Handbook of Mineralogy.
8. Arnold 2005
9. Apparently a different river than Popovka (Kolyma) in the Russian Far East.
10. Wiersma 1970, pp. 36–43
11. Kogel, J.E. (2006). Industrial Minerals & Rocks: Commodities, Markets, and Uses. Society for Mining, Metallurgy, and Exploration. ISBN 978-0-87335-233-8. Retrieved 30 Aug 2024. Page 375.
12. "3.10 Drilling Fluids Summary" (PDF). npd.no. Sokkeldirektoratet, Norway. Archived from the original (PDF) on 2018-01-01. Retrieved 2024-08-30.
13. Ferraz, Eduardo; Alves, Luís; Sanguino, Pedro; Santarén, Julio; Rasteiro, Maria G.; Gamelas, José A. F. (January 2021). "Stabilization of Palygorskite Aqueous Suspensions Using Bio-Based and Synthetic Polyelectrolytes". Polymers. 13 (1): 129. doi:10.3390/polym13010129. PMC 7795911. PMID 33396903.
14. Almeida, Ricardo; Ferraz, Eduardo; Santarén, Julio; Gamelas, José A. F. (June 2021). "Comparison of Surface Properties of Sepiolite and Palygorskite: Surface Energy and Nanoroughness". Nanomaterials. 11 (6): 1579. doi:10.3390/nano11061579. PMC 8235428. PMID 34208459.
15. "Attapulgite Tablet". drugs.com. Drugsite Trust, Auckland, New Zealand. Retrieved 30 August 2024.
16. "Antidiarrheal Drug Products for Overthe-Counter Human Use; Final Monograph" (PDF). FDA. Archived from the original (PDF) on 31 October 2004. Retrieved 30 August 2024.
17. "Kaopectate reformulation and upcoming labeling changes" (PDF). fda.gov. Archived from the original (PDF) on 2022-01-15. Retrieved 30 August 2024.
18. "Kaopectate Reformulation Causes Confusion" (PDF). FDA Patient Safety News. October 2004. Show #32. Archived from the original (PDF) on 24 October 2016.
19. Andrejkovičová, S.; Velosa, A.; Gameiro, A.; Ferraz, E.; Rocha, F. (2013). "Palygorskite as an admixture to air lime–metakaolin mortars for restoration purposes". Applied Clay Science. 83–84: 368–374. Bibcode:2013ApCS...83..368A. doi:10.1016/j.clay.2013.07.020.
20. See abstract of Arnold (2005).
21. Haude (1997).
22. Arnold and Bohor (1975), as cited in Haude (1997).

References

• Arnold, Dean E.; Bohor, Bruce F. (1975). "Attapulgite and Maya Blue: an Ancient Mine Comes to Light". Archaeology. 28 (1): 23–29. ISSN 0003-8113. JSTOR 41685610. OCLC 9974148442.
• Arnold, Dean E. (2005). "Maya Blue and Palygorskite: A second possible pre-Columbian source". Ancient Mesoamerica. 16 (1): 51–62. doi:10.1017/S0956536105050078. ISSN 0956-5361. JSTOR 26309393. OCLC 9977998608. S2CID 162864157. Maya Blue is an unusual blue pigment used on pottery, sculpture, and murals from the Preclassic to the Colonial period. Until the late 1960s, its composition was unknown, but chemists working in Spain, Belgium, Mexico, and the United States identified Maya Blue as a combination of indigo and the unusual clay mineral palygorskite (also called attapulgite).
• Garcia-Rivas, Javier; Sánchez del Río, Manuel; García-Romero, Emilia; Suárez, Mercedes (2017). "An insight in the structure of a palygorskite from Palygorskaja: Some questions on the standard model". Applied Clay Science. 148: 39–47. Bibcode:2017ApCS..148...39G. doi:10.1016/j.clay.2017.08.006. ISSN 0169-1317. OCLC 7121090747. This palygorskite is consistent with a purely orthorhombic palygorskite, based on good agreement of data with simulations.
• Haude, Mary Elizabeth (1997). "Identification and Classification of Colorants Used During Mexico's Early Colonial Period". The Book and Paper Group Annual. 16. doi:10.2307/3179811. ISSN 0887-8978. JSTOR 3179811. OCLC 882603996. Retrieved 2007-03-14.
• Wiersma, J. (1970). Provenance, genesis and paleogeographical implications of microminerals occurring in sedimentary rocks of the Jordan Valley area. Publicaties van het Fysisch Geografisch en Bodemkundig Laboratorium van de Universiteit van Amsterdam. hdl:11245.1/9c960a65-cab0-44de-9e20-9deae0260fe3. OCLC 898805873. PhD Thesis, Faculty of Science, University of Amsterdam.

Further literature

• Callen, Roger E. (1984). "Clays of the Palygorskite-Sepiolite Group: Depositional Environment, Age and Distribution". In Singer, A.; Galan, E. (eds.). Palygorskite — Sepiolite: Occurrences, Genesis and Uses. Developments in Sedimentology. Vol. 37. Amsterdam, New York: Elsevier. pp. 1–37. doi:10.1016/S0070-4571(08)70027-X. ISBN 9780444423375. OCLC 10606245.
• Kazakov, Alexander Vasilievich (1911). "Материалы к изучению группы палыгорскита" [Materials to the study of the palygorskite group]. Изв. ИАН (Izvestiia Imperatorsko Akademii Nauk, Bulletin of the Imperial Academy of Sciences. 6. 5 (9). Saint Petersburg: 679–694. OCLC 212413675.
• Weaver, Charles E.; Pollard, Lin D. (1973). The chemistry of clay minerals. Amsterdam: Elsevier Scientific Pub. Co. ISBN 9780444410436. OCLC 713936.
• Zelazny L, Calhoun F (1977). "Palygorskite (attapulgite), sepiolite, talc, pyrophyllite, and zeolites". In Dixon JB, Weed SB, Dinauer RC (eds.). Minerals in soil environments. Madison, Wisconsin: Soil Science Society of America. pp. 435–470. ISBN 9780891187653. OCLC 3574957. Retrieved 30 August 2024. Abstract. The structural properties and identification, natural occurrence, equilibrium environment and conditions for synthesis, chemical and physical properties, and quantitative determination of these minerals are considered.
• Zvyagin, B.B.; Mishchenko, K.S.; Shitov, V.A. (1963). "Electron diffraction data on the structure of sepiolite and palygorskite". Crystallography Reports (Soviet Physics Crystallography, Kristallografya). 8. American Institute of Physics: 148–153. ISSN 1063-7745. OCLC 26141038.

External links

• International Chemical Safety Card 1321
• "Purified attapulgite clay. Abstrict [sic]". patentinformationsearch.com. Patent Information Search. 2012. Archived from the original on 2013-06-23. Retrieved 29 August 2024. Attapulgite clay patent.
• Seibert, David. "Decatur County Historical Markers. Attapulgite". Galileo. Georgia's virtual library. University System of Georgia. Archived from the original on 2016-11-15. Retrieved 29 August 2024.