Clay minerals form in the presence of water and have been important to life, and many theories of abiogenesis involve them. They are important constituents of soils, and have been useful to humans since ancient times in agriculture and manufacturing.
Clay is a very fine-grained geologic material that develops plasticity when wet, but becomes hard, brittle and non–plastic upon drying or firing. It is a very common material, and is the oldest known ceramic. Prehistoric humans discovered the useful properties of clay and used it for making pottery. The chemistry of clay, including its capacity to retain nutrient cations such as potassium and ammonium, is important to soil fertility.
Because the individual particles in clay are less than 4 micrometers (0.00016 in) in size, they cannot be characterized by ordinary optical or physical methods. The crystallographic structure of clay minerals became better understood in the 1930s with advancements in the x-ray diffraction (XRD) technique indispensable to deciphering their crystal lattice. Clay particles were found to be predominantly sheet silicate (phyllosilicate) minerals, now grouped together as clay minerals. Their structure is based on flat hexagonal sheets similar to those of the mica group of minerals. Standardization in terminology arose during this period as well, with special attention given to similar words that resulted in confusion, such as sheet and plane.
Because clay minerals are usually (but not necessarily) ultrafine-grained, special analytical techniques are required for their identification and study. In addition to X-ray crystallography, these include electron diffraction methods, various spectroscopic methods such as Mössbauer spectroscopy, infrared spectroscopy, Raman spectroscopy, and SEM-EDS or automated mineralogy processes. These methods can be augmented by polarized light microscopy, a traditional technique establishing fundamental occurrences or petrologic relationships.
Clay minerals are common weathering products (including weathering of feldspar) and low-temperature hydrothermal alteration products. Clay minerals are very common in soils, in fine-grained sedimentary rocks such as shale, mudstone, and siltstone and in fine-grained metamorphic slate and phyllite.
Given the requirement of water, clay minerals are relatively rare in the Solar System, though they occur extensively on Earth where water has interacted with other minerals and organic matter. Clay minerals have been detected at several locations on Mars, including Echus Chasma, Mawrth Vallis, the Memnonia quadrangle and the Elysium quadrangle. Spectrography has confirmed their presence on asteroids including the dwarf planet Ceres and Tempel 1, as well as Jupiter's moon Europa.
Like all phyllosilicates, clay minerals are characterised by two-dimensional sheets of corner-sharing SiO4 tetrahedra or AlO4 octahedra. The sheet units have the chemical composition (Al, Si)3O4. Each silica tetrahedron shares three of its vertex oxygen ions with other tetrahedra, forming a hexagonal array in two dimensions. The fourth oxygen ion is not shared with another tetrahedron and all of the tetrahedra "point" in the same direction; i.e. all of the unshared oxygen ions are on the same side of the sheet. These unshared oxygen ions are called apical oxygen ions.
In clays, the tetrahedral sheets are always bonded to octahedral sheets formed from small cations, such as aluminum or magnesium, and coordinated by six oxygen atoms. The unshared vertex from the tetrahedral sheet also forms part of one side of the octahedral sheet, but an additional oxygen atom is located above the gap in the tetrahedral sheet at the center of the six tetrahedra. This oxygen atom is bonded to a hydrogen atom forming an OH group in the clay structure. Clays can be categorized depending on the way that tetrahedral and octahedral sheets are packaged into layers. If there is only one tetrahedral and one octahedral group in each layer the clay is known as a 1:1 clay. The alternative, known as a 2:1 clay, has two tetrahedral sheets with the unshared vertex of each sheet pointing towards each other and forming each side of the octahedral sheet.
Bonding between the tetrahedral and octahedral sheets requires that the tetrahedral sheet becomes corrugated or twisted, causing ditrigonal distortion to the hexagonal array, and the octahedral sheet is flattened. This minimizes the overall bond-valence distortions of the crystallite.
Depending on the composition of the tetrahedral and octahedral sheets, the layer will have no charge or will have a net negative charge. If the layers are charged this charge is balanced by interlayer cations such as Na+ or K+ or by a lone octahedral sheet. The interlayer may also contain water. The crystal structure is formed from a stack of layers interspaced with the interlayers.
Clay minerals can be classified as 1:1 or 2:1. A 1:1 clay would consist of one tetrahedral sheet and one octahedral sheet, and examples would be kaolinite and serpentinite. A 2:1 clay consists of an octahedral sheet sandwiched between two tetrahedral sheets, and examples are talc, vermiculite, and montmorillonite. The layers in 1:1 clays are uncharged and are bonded by hydrogen bonds between layers, but 2:1 layers have a net negative charge and may be bonded together either by individual cations (such as potassium in illite or sodium or calcium in smectites) or by positively charged octahedral sheets (as in chlorites).
Clay minerals include the following groups:
- Kaolin group which includes the minerals kaolinite, dickite, halloysite, and nacrite (polymorphs of Al2Si2O5(OH)4).
- Smectite group which includes dioctahedral smectites, such as montmorillonite, nontronite and beidellite, and trioctahedral smectites, such as saponite. In 2013, analytical tests by the Curiosity rover found results consistent with the presence of smectite clay minerals on the planet Mars.
- Illite group which includes the clay-micas. Illite is the only common mineral in this group.
- Chlorite group includes a wide variety of similar minerals with considerable chemical variation.
- Other 2:1 clay types exist such as palygorskite (also known as attapulgite) and sepiolite, clays with long water channels internal to their structure.
Mixed layer clay variations exist for most of the above groups. Ordering is described as a random or regular order and is further described by the term reichweite, which is German for range or reach. Literature articles will refer to an R1 ordered illite-smectite, for example. This type would be ordered in an illite-smectite-illite-smectite (ISIS) fashion. R0 on the other hand describes random ordering, and other advanced ordering types are also found (R3, etc.). Mixed layer clay minerals which are perfect R1 types often get their own names. R1 ordered chlorite-smectite is known as corrensite, R1 illite-smectite is rectorite.
|Clay||Kaolinite||Dehydrated halloysite||Hydrated halloysite||Illite||Vermiculite||Smectite||Chlorite|
|CEC (meq/100 g)||3||12||12||25||150||85||40|
|DTA||End. 500–660° + Sharp* Exo. 900–975° Sharp||Same as kaolinite but 600° peak slope ratio > 2.5||Same as kaolinite but 600° peak slope ratio > 2.5||End. 500–650° Broad. End. 800–900° Broad Exo. 950°||0||End. 600–750° End. 900°. Exo. 950°||End. 610 ± 10° or 720 ± 20°|
X-ray rf(001) is the spacing between layers in nanometers, as determined by X-ray crystallography. Glycol (mg/g) is the adsorption capacity for glycol, which occupies the interlayer sites when the clay is exposed to a vapor of ethylene glycol at 60 °C (140 °F) for eight hours. CEC is the cation exchange capacity of the clay. K2O (%) is the percent content of potassium oxide in the clay. DTA describes the differential thermal analysis curve of the clay.
Clay and the origins of life
Biomedical applications of clays
The structural and compositional versatility of clay minerals gives them interesting biological properties. Due to disc-shaped and charged surfaces, clay interacts with a range of drugs, protein, polymers, DNA, or other macromolecules. Some of the applications of clays include drug delivery, tissue engineering, and bioprinting.
Clay minerals can be incorporated in lime-metakaolin mortars to improve mechanical properties. Electrochemical separation helps to obtain modified saponite-containing products with high smectite-group minerals concentrations, lower mineral particles size, more compact structure, and greater surface area. These characteristics open possibilities for the manufacture of high-quality ceramics and heavy-metal sorbents from saponite-containing products. Furthermore, tail grinding occurs during the preparation of the raw material for ceramics; this waste reprocessing is of high importance for the use of clay pulp as a neutralizing agent, as fine particles are required for the reaction. Experiments on the histosol deacidification with the alkaline clay slurry demonstrated that neutralization with the average pH level of 7.1 is reached at 30% of the pulp added and an experimental site with perennial grasses proved the efficacy of the technique. Moreover, the reclamation of disturbed lands is an integral part of the social and environmental responsibility of the mining company and this scenario addresses the community necessities at both local and regional levels.
- Clay chemistry – The chemical structures, properties and reactions of clay minerals
- Expansive clay – Clay soil with high smectite content and prone to swelling and shrinking
- Mudstone/clays on planet Mars
- Reverse weathering
- The Clay Minerals Society
- Clay mineral X-ray diffraction
- Modeling clay
- Kerr PF (1952). "Formation and Occurrence of Clay Minerals". Clays and Clay Minerals. 1 (1): 19–32. doi:10.1346/CCMN.1952.0010104.
- Guggenheim & Martin 1995, pp. 255–256. sfn error: no target: CITEREFGuggenheimMartin1995 (help)
- Science Learning Hub 2010. sfn error: no target: CITEREFScience_Learning_Hub2010 (help)
- Breuer 2012. sfn error: no target: CITEREFBreuer2012 (help)
- Boggs 2006, p. 140. sfn error: no target: CITEREFBoggs2006 (help)
- Scarre 2005, p. 238. sfn error: no target: CITEREFScarre2005 (help)
- Hodges, S.C. (2010). "Soil fertility basics" (PDF). Soil Science Extension, North Carolina State University. Retrieved 8 December 2020.
- Bailey SW (1980). "Summary of recommendations of AIPEA nomenclature committee on clay minerals". Am. Mineral. 65: 1–7.
- Nesse, William D. (2000). Introduction to mineralogy. New York: Oxford University Press. pp. 252–257. ISBN 9780195106916.
- Środoń, J. (2006). "Chapter 12.2 Identification and Quantitative Analysis of Clay Minerals". Developments in Clay Science. 1: 765–787. doi:10.1016/S1572-4352(05)01028-7.
- Murad, Enver (1998). "Clays and clay minerals: What can Mössbauer spectroscopy do to help understand them?". Hyperfine Interactions. 117 (1/4): 39–70. doi:10.1023/A:1012635124874.
- Kloprogge, J.T. (2017). "Raman Spectroscopy of Clay Minerals". Developments in Clay Science. 8: 150–199. doi:10.1016/B978-0-08-100355-8.00006-0.
- Rajkumar, K.; Ramanathan, A. L.; Behera, P. N. (September 2012). "Characterization of clay minerals in the Sundarban mangroves river sediments by SEM/EDS". Journal of the Geological Society of India. 80 (3): 429–434. doi:10.1007/s12594-012-0161-5.
- Weaver, R. (2003). "Rediscovering polarized light microscopy" (PDF). American Laboratory. 35 (20): 55–61. Retrieved 20 September 2021.
- Georgia Institute of Technology (20 Dec 2012). "Clays on Mars: More plentiful than expected". Science Daily. Retrieved 22 March 2019.
- Rivkin AS, Volquardsen EL, Clark BE (2006). "The surface composition of Ceres: Discovery of carbonates and iron-rich clays" (PDF). Icarus. 185 (2): 563–567. doi:10.1016/j.icarus.2006.08.022.
- Napier WM, Wickramasinghe JT, Wickramasinghe NC (2007). "The origin of life in comets". Int. J. Astrobiol. 6 (4): 321–323. doi:10.1017/S1473550407003941.
- Greicius T (26 May 2015). "Clay-Like Minerals Found on Icy Crust of Europa". NASA.
- Nesse 2000, pp. 235–237.
- "The Clay Mineral Group". Amethyst Galleries. 1996. Archived from the original on 27 December 2005. Retrieved 22 February 2007.
- Agle DC, Brown D (12 March 2013). "NASA Rover Finds Conditions Once Suited for Ancient Life on Mars". NASA. Retrieved 12 March 2013.
- Wall M (12 March 2013). "Mars Could Once Have Supported Life: What You Need to Know". Space.com. Retrieved 12 March 2013.
- Chang K (12 March 2013). "Mars Could Once Have Supported Life, NASA Says". The New York Times. Retrieved 12 March 2013.
- Moore DM, Reynolds Jr RC (1997). X-Ray Diffraction and the Identification and Analysis of Clay Minerals (2nd ed.). Oxford: Oxford University Press. ISBN 9780195087130. OCLC 34731820.
- Fundamentals of Soil Behavior, 3rd Edition James K. Mitchell, Kenichi Soga. ISBN 978-0-471-46302-3, Table 3.9.
- Cairns-Smith, Graham (2 September 1982). Genetic Takeover and the Mineral Origins of Life. Cambridge: Cambridge University Press. ISBN 0-521-23312-7. OCLC 7875600.
- Dawkins 1996, pp. 148–161 harvnb error: no target: CITEREFDawkins1996 (help)
- Huang, Wenhua; Ferris, James P. (12 July 2006). "One-Step, Regioselective Synthesis of up to 50-mers of RNA Oligomers by Montmorillonite Catalysis". Journal of the American Chemical Society. 128 (27): 8914–8919. doi:10.1021/ja061782k. PMID 16819887.
- Subramaniam, Anand Bala; Wan, Jiandi; Gopinath, Arvind; Stone, Howard A. (2011). "Semi-permeable vesicles composed of natural clay" (PDF). Soft Matter. 7 (6): 2600–2612. arXiv:1011.4711. Bibcode:2011SMat....7.2600S. doi:10.1039/c0sm01354d. S2CID 52253528.
- Hartman, Hyman (1998). "Photosynthesis and the Origin of Life". Origins of Life and Evolution of Biospheres. 28 (4–6): 515–521. Bibcode:1998OLEB...28..515H. doi:10.1023/A:1006548904157. PMID 11536891. S2CID 2464.
- Chrzanowski, Wojciech; Kim, Sally Yunsun; Abou Neel, Ensanya Ali (2013). "Biomedical Applications of Clay". Australian Journal of Chemistry. 66 (11): 1315. doi:10.1071/CH13361.
- Andrejkovičová, S.; Velosa, A.L.; Ferraz, E.; Rocha, F. (2014). "Influence of clay minerals addition on mechanical properties of air lime–metakaolin mortars". Construction and Building Materials. 65: 132–139. doi:10.1016/j.conbuildmat.2014.04.118.
- Chanturiya, V.A.; Minenko, V.G.; Makarov, D.V. (2018). "Advanced Techniques of Saponite Recovery from Diamond Processing Plant Water and Areas of Saponite Application". Minerals. 8 (12): 549. doi:10.3390/min8120549. This article incorporates text available under the CC BY 4.0 license.
- Pashkevich, M.A.; Alekseenko, A.V. (2020). "Reutilization Prospects of Diamond Clay Tailings at the Lomonosov Mine, Northwestern Russia". Minerals. 10 (6): 517. doi:10.3390/min10060517. This article incorporates text available under the CC BY 4.0 license.