Chemistry:Palygorskite

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Palygorskite
A sample of palygorskite from Hnúšťa, Slovakia.
General
CategoryPhyllosilicate minerals[1][2]
Formula
(repeating unit)		(Mg,Al)
2Si
4O
10(OH) · 4(H
2O) Al2Mg2◻2Si8O20(OH)2(H2O)4 · 4H2O[3]
Strunz classification9.EE.20[3]
Crystal systemMonoclinic,[3] orthorhombic[4]
Crystal classPrismatic (2/m)[3]
(same H-M symbol)
Space groupB2/m and setting C2/m,[3] P 21 21 21[5]
Unit cella = 12.78 Å, b = 17.86 Å,
c = 5.24 Å; β = 95.78°; Z = 4[3]
Identification
ColorWhite, grayish, yellowish, gray-green[3]
Crystal habitCommonly fibrous (asbestiform), tangled mats known as mountain leather. Individual, small crystals are lath-shaped[3]
CleavageDistinct/good, good on {110}[3]
TenacityTough[3]
Mohs scale hardness2 – 2.5[3]
|re|er}}Waxy, earthy[3]
DiaphaneityTranslucent[3]
Specific gravity1 – 2.6[3]
Density2.1 - 2.6 g/cm3 (Measured); 2.35 g/cm3 (Calculated)[3]
Optical propertiesBiaxial (−)[3]
Refractive indexnα = 1.522 – 1.528 nβ = 1.530 – 1.546 nγ = 1.533 – 1.548[3]
Birefringenceδ = 0.011 – 0.020[3]
PleochroismX= pale yellow Y=Z= pale yellow-green[3]
Common impuritiesFe,K [3]
References[1][2][3][6]

Palygorskite or attapulgite is a magnesium aluminium phyllosilicate with the chemical formula (Mg,Al)
2Si
4O
10(OH) · 4(H
2O) 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][6] 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.

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]

Potential toxicity

Studies have shown that Palygorskite may be carcinogenic to humans. Much like asbestos and some fibrous zeolites, Palygorskite can be found in asbestiform habits.[15]

Studies thus far on the possibility of Palygorskite being a carcinogen has been mixed. Some studies show that cytotoxicity in rats, mice, livestock, hamsters, and even humans have caused malignant mesothelioma. In rats specifically, studies have ranged from 2.5-94% mesothelioma rates. Differences in palygorskite fiber length and purity (i.e., presence of other carcinogenic mineral fibers) may have been responsible for the disparate results observed in those experiments.[16]

Specifically in Nevada, there is a strong link between Palygorskite and mesothelioma. In 2011, medical Geologist Brenda Buck of The University of Nevada Las Vegas (UNLV) was looking for arsenic minerals in Nellis Dunes. What she found was fibrous Palgorskite in her sample.[17] Further research found that more women and children than men had higher rates of malignant mesothelioma; with the ratio being as high as 3:1. Palygorskite samples were taken from 4 different locations in southern Nevada, and scanned by electron microscopy (SEM). The results showed that Palygorskite fibrous physical features similar to those of asbestos minerals.[16][18]

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.[19] 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.[20][21] The manufacturer also settled with the State of California over toxic levels of lead in the attapulgite component. Part of this settlement was a reformulation to remove attapulgite in the liquid version in the US.[22]

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.[23] 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.[24]

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.[25]

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.[26] Human sacrificial victims in postclassic Mesoamerica were frequently daubed with this blue pigmentation.[27]

  • Electron diffractogram of palygorskite (Wiersma 1970).
    Electron diffractogram of palygorskite (Wiersma 1970).
  • Electron micrograph 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.
    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.
    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.
    Palygorskite. Estonian Museum of Natural History, 2015.

See also

Notes

  1. ↑ 1.0 1.1 "Palygorskite Mineral Data". David Barthelmy. 2024. http://www.webmineral.com/data/Palygorskite.shtml. 
  2. ↑ 2.0 2.1 2.2 Lu, Yushen; Wang, Aiqin (2022). "From structure evolution of palygorskite to functional material: A review". Microporous and Mesoporous Materials 333. doi:10.1016/j.micromeso.2022.111765. Bibcode: 2022MicMM.33311765L. https://www.sciencedirect.com/science/article/abs/pii/S1387181122000865. Retrieved 20 September 2009. 
  3. ↑ 3.00 3.01 3.02 3.03 3.04 3.05 3.06 3.07 3.08 3.09 3.10 3.11 3.12 3.13 3.14 3.15 3.16 3.17 3.18 3.19 3.20 3.21 3.22 "Palygorskite. A valid IMA mineral species - grandfathered". Hudson Institute of Mineralogy. 2024. http://www.mindat.org/min-3072.html. 
  4. ↑ Garcia-Rivas et al. 2017.
  5. ↑ Wiersma 1970, p. 87.
  6. ↑ 6.0 6.1 "Palygorskite (Mg,Al)2 Si4 O10 (OH).4H2O". Mineral Data Publishing, version 1.2. 2001. http://www.handbookofmineralogy.com/pdfs/palygorskite.pdf.  Palygorskite in the Handbook of Mineralogy.
  7. ↑ Warr, L.N. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine 85 (3): 291–320. doi:10.1180/mgm.2021.43. Bibcode: 2021MinM...85..291W. 
  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. https://books.google.com/books?id=zNicdkuulE4C&pg=PA375. Retrieved 30 August 2024.  Page 375.
  12. ↑ "3.10 Drilling Fluids Summary". Sokkeldirektoratet, Norway. http://www.npd.no/engelsk/cwi/pbl/geochemical_pdfs/1836_1.pdf. 
  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" (in en). Polymers 13 (1): 129. doi:10.3390/polym13010129. 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" (in en). Nanomaterials 11 (6): 1579. doi:10.3390/nano11061579. PMID 34208459. 
  15. ↑ Belluso, E.; Cavallo, A; Halterman, D. (January 2017). Gualtieri, A.F.. ed (in en). Crystal habit of mineral fibres. European Mineralogy Union. pp. 65–109. https://www.researchgate.net/publication/318295435. Retrieved 29 November 2025. 
  16. ↑ 16.0 16.1 Larson, David; Powers, Amy; Ambrosi, Jean-Paul; Tanji, Mika; Napolitano, Andrea; Flores, Erin G.; Baumann, Francine; Pellegrini, Laura et al. (17 August 2016). "Investigating palygorskite's role in the development of mesothelioma in southern Nevada: Insights into fiber-induced carcinogenicity" (in en). Journal of Toxicology and Environmental Health, Part B 19 (5–6): 213–230. doi:10.1080/10937404.2016.1195321. PMID 27705545. Bibcode: 2016JTEHB..19..213L. 
  17. ↑ Sever, Megan (29 January 2015). "Asbestos found in Nevada and Arizona: Roadblock and potential health hazard?". www.earthmagazine.org. Earth the Science behind the headlines (Las Vegas, Nevada). https://www.earthmagazine.org/article/asbestos-found-nevada-and-arizona-roadblock-and-potential-health-hazard. 
  18. ↑ Baumann, Francine; Buck, Brenda J.; Metcalf, Rodney V.; McLaurin, Brett T.; Merkler, Douglas J.; Carbone, Michele (May 2015). "The Presence of Asbestos in the Natural Environment is Likely Related to Mesothelioma in Young Individuals and Women from Southern Nevada" (in en). Journal of Thoracic Oncology 10 (5): 731–737. doi:10.1097/JTO.0000000000000506. PMID 25668121. 
  19. ↑ "Attapulgite Tablet". Auckland, New Zealand: Drugsite Trust. https://www.drugs.com/cons/diasorb.html. 
  20. ↑ "Antidiarrheal Drug Products for Overthe-Counter Human Use; Final Monograph". https://www.fda.gov/OHRMS/DOCKETS/98fr/03-9380.pdf. 
  21. ↑ "Kaopectate reformulation and upcoming labeling changes.". https://www.fda.gov/downloads/drugs/drugsafety/medicationerrors/ucm080666.pdf. 
  22. ↑ Kay, Jane (27 June 2003). "Lead to be removed from Kaopectate diarrhea drug". SFGate. https://www.sfgate.com/health/article/Lead-to-be-removed-from-Kaopectate-diarrhea-drug-2577149.php. 
  23. ↑ "Kaopectate Reformulation Causes Confusion". October 2004. http://www.fda.gov/downloads/Safety/FDAPatientSafetyNews/UCM417802.pdf. 
  24. ↑ Andrejkovičová, S.; Velosa, A.; Gameiro, A.; Ferraz, E.; Rocha, F. (2013). "Palygorskite as an admixture to air lime–metakaolin mortars for restoration purposes" (in en). Applied Clay Science 83–84: 368–374. doi:10.1016/j.clay.2013.07.020. Bibcode: 2013ApCS...83..368A. 
  25. ↑ See abstract of Arnold 2005
  26. ↑ Haude 1997.
  27. ↑ Arnold & 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. 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. OCLC 9977998608. "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. doi:10.1016/j.clay.2017.08.006. ISSN 0169-1317. OCLC 7121090747. Bibcode: 2017ApCS..148...39G. "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. OCLC 882603996. http://aic.stanford.edu/sg/bpg/annual/v16/bp16-05.html. Retrieved 14 March 2007. 
  • Wiersma, J. (1970). Provenance, genesis and paleogeographical implications of microminerals occurring in sedimentary rocks of the Jordan Valley area (PhD thesis). Publicaties van het Fysisch Geografisch en Bodemkundig Laboratorium van de Universiteit van Amsterdam. University of Amsterdam. hdl:11245.1/9c960a65-cab0-44de-9e20-9deae0260fe3. OCLC 898805873.

Further reading

  • Callen, Roger E. (1984). "Clays of the Palygorskite-Sepiolite Group: Depositional Environment, Age and Distribution". Palygorskite — Sepiolite: Occurrences, Genesis and Uses. Developments in Sedimentology. 37. Amsterdam, New York: Elsevier. pp. 1–37. doi:10.1016/S0070-4571(08)70027-X. ISBN 978-0-444-42337-5. OCLC 10606245. 
  • Kazakov, Alexander Vasilievich (1911). "Материалы к изучению группы палыгорскита". Изв. ИАН (Izvestiia Imperatorsko Akademii Nauk, Bulletin of the Imperial Academy of Sciences. 6 (Saint Petersburg) 5 (9): 679–694. OCLC 212413675. 
  • Weaver, Charles E.; Pollard, Lin D. (1973). The chemistry of clay minerals. Amsterdam: Elsevier Scientific Pub. Co.. ISBN 978-0-444-41043-6. OCLC 713936. 
  • Zelazny, L.W.; Calhoun, F.G. (1977). "Palygorskite (attapulgite), sepiolite, talc, pyrophyllite, and zeolites". Minerals in soil environments. Madison, Wisconsin: Soil Science Society of America. pp. 435–470. ISBN 978-0-89118-765-3. OCLC 3574957. https://archive.org/details/mineralsinsoilen0000unse_x1p0. 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) (American Institute of Physics) 8: 148–153. ISSN 1063-7745. OCLC 26141038. 



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