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60-484: The Fort St. John Group is mostly composed of dark shale deposited in a marine environment. Bentonite is present in the shale, and it is interbedded with sandstone , siltstone and conglomerates . The Fort St. John Group occurs in the subsurface in the Peace River Country of northeastern British Columbia and north-western Alberta , in southern Yukon and southern Northwest Territories . It has

120-564: A basaltic rock in Kivu ( Zaïre ), they noted how the occurrence of kaolinite depended on the "degrée de drainage" of the area involved. A clear distinction was found between areas with good drainage (i.e., areas with a marked difference between wet and dry seasons) and those areas with poor drainage (i.e., perennially swampy areas). Kaolinite was only found in the areas with distinct seasonal alternations between wet and dry. The possible significance of alternating wet and dry conditions on

180-418: A 1:1 or TO clay mineral because its crystals consist of stacked TO layers. Each TO layer consists of a tetrahedral ( T ) sheet composed of silicon and oxygen ions bonded to an octahedral ( O ) sheet composed of oxygen, aluminium, and hydroxyl ions. The T sheet is so called because each silicon ion is surrounded by four oxygen ions forming a tetrahedron. The O sheet is so called because each aluminium ion

240-405: A compacted and massive form of kaolin. The chemical formula for kaolinite as written in mineralogy is Al 2 Si 2 O 5 (OH) 4 , however, in ceramics applications the same formula is typically written in terms of oxides, thus giving Al 2 O 3 ·2SiO 2 ·2H 2 O . Compared with other clay minerals, kaolinite is chemically and structurally simple. It is described as

300-414: A hard, fissile, metamorphic rock known as slate . With continued increase in metamorphic grade the sequence is phyllite , then schist and finally gneiss . Shale is the most common source rock for hydrocarbons ( natural gas and petroleum ). The lack of coarse sediments in most shale beds reflects the absence of strong currents in the waters of the depositional basin. These might have oxygenated

360-417: A lack of convincing results in their own experiments, La Iglesia and Van Oosterwijk-Gastuche (1978) had to conclude, however, that there were other, still unknown, factors involved in the low-temperature nucleation of kaolinite. Because of the observed very slow crystallization rates of kaolinite from solution at room temperature Fripiat and Herbillon (1971) postulated the existence of high activation energies in

420-414: A layer structure. From the following equation (as given by Gastuche and DeKimpe, 1962) for kaolinite formation it can be seen that five molecules of water must be removed from the reaction for every molecule of kaolinite formed. Field evidence illustrating the importance of the removal of water from the kaolinite reaction has been supplied by Gastuche and DeKimpe (1962). While studying soil formation on

480-611: A low shrink–swell capacity and a low cation-exchange capacity (1–15 meq/100 g). Rocks that are rich in kaolinite, and halloysite , are known as kaolin ( / ˈ k eɪ . ə l ɪ n / ) or china clay . In many parts of the world kaolin is colored pink-orange-red by iron oxide , giving it a distinct rust hue. Lower concentrations of iron oxide yield the white, yellow, or light orange colors of kaolin. Alternating lighter and darker layers are sometimes found, as at Providence Canyon State Park in Georgia, United States. Kaolin

540-492: A review on the formation of kaolinite, raised the fundamental question how a disordered material (i.e., the amorphous fraction of tropical soils) could ever be transformed into a corresponding ordered structure. This transformation seems to take place in soils without major changes in the environment, in a relatively short period of time, and at ambient temperature (and pressure ). Low-temperature synthesis of clay minerals (with kaolinite as an example) has several aspects. In

600-419: A series of alternations of periodically changing conditions (by definition, taking place in an open system) will bring about the low-temperature formation of more and more of the stable phase kaolinite instead of (ill-defined) amorphous alumino-silicates. In 2009, up to 70% of kaolin was used in the production of paper . Following reduced demand from the paper industry, resulting from both competing minerals and

660-586: A thickness of 700 metres (2,300 ft) to 2,000 metres (6,560 ft). The Fort St. John Group is conformably overlain by the Dunvegan Formation and conformably underlain by the Bullhead Group or may rest disconformably on older units. The Fort St. John Group is subdivided into the following formations: *Buckinghorse Formation is equivalent to the sum of Lepine Formation, Scatter Formation and Garbutt Formation. It occurs north-east of

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720-1201: Is accompanied by telogenesis , the third and final stage of diagenesis. As erosion reduces the depth of burial, renewed exposure to meteoric water produces additional changes to the shale, such as dissolution of some of the cement to produce secondary porosity . Pyrite may be oxidized to produce gypsum . Black shales are dark, as a result of being especially rich in unoxidized carbon . Common in some Paleozoic and Mesozoic strata , black shales were deposited in anoxic , reducing environments, such as in stagnant water columns. Some black shales contain abundant heavy metals such as molybdenum , uranium , vanadium , and zinc . The enriched values are of controversial origin, having been alternatively attributed to input from hydrothermal fluids during or after sedimentation or to slow accumulation from sea water over long periods of sedimentation. Fossils , animal tracks or burrows and even raindrop impressions are sometimes preserved on shale bedding surfaces. Shales may also contain concretions consisting of pyrite, apatite , or various carbonate minerals. Shales that are subject to heat and pressure of metamorphism alter into

780-419: Is an important raw material in many industries and applications. Commercial grades of kaolin are supplied and transported as powder, lumps, semi-dried noodle or slurry . Global production of kaolin in 2021 was estimated to be 45 million tonnes, with a total market value of US $ 4.24 billion. The English name kaolin was borrowed in 1727 from François Xavier d'Entrecolles 's 1712 French reports on

840-510: Is called the "white gold" belt; Sandersville is known as the "Kaolin Capital of the World" due to its abundance of kaolin. In the late 1800s, an active kaolin surface-mining industry existed in the extreme southeast corner of Pennsylvania, near the towns of Landenberg and Kaolin , and in what is present-day White Clay Creek Preserve. The product was brought by train to Newark, Delaware , on

900-420: Is characterized by its tendency to split into thin layers ( laminae ) less than one centimeter in thickness. This property is called fissility . Shale is the most common sedimentary rock. The term shale is sometimes applied more broadly, as essentially a synonym for mudrock , rather than in the narrower sense of clay-rich fissile mudrock. Shale typically exhibits varying degrees of fissility. Because of

960-638: Is composed of about 58% clay minerals, 28% quartz, 6% feldspar , 5% carbonate minerals, and 2% iron oxides . Most of the quartz is detrital (part of the original sediments that formed the shale) rather than authigenic (crystallized within the shale after deposition). Shales and other mudrocks contain roughly 95 percent of the organic matter in all sedimentary rocks. However, this amounts to less than one percent by mass in an average shale. Black shales, which form in anoxic conditions, contain reduced free carbon along with ferrous iron (Fe ) and sulfur (S ). Amorphous iron sulfide , along with carbon, produce

1020-430: Is evidence that shale acts as a semipermeable medium, allowing water to pass through while retaining dissolved salts. The fine particles that compose shale can remain suspended in water long after the larger particles of sand have been deposited. As a result, shales are typically deposited in very slow moving water and are often found in lakes and lagoonal deposits, in river deltas , on floodplains and offshore below

1080-407: Is lost. Above around 400 °C hydroxyl ions (OH ) are lost from the kaolinite crystal structure in the form of water: the material cannot now be plasticised by absorbing water. This is irreversible, as are subsequent transformations; this is referred to as calcination . Endothermic dehydration of kaolinite begins at 550–600 °C producing disordered metakaolin , but continuous hydroxyl loss

1140-455: Is more likely to form nonfissile mudstone than shale. On the other hand, black shales often have very pronounced fissility ( paper shales ) due to binding of hydrocarbon molecules to the faces of the clay particles, which weakens the binding between particles. Lithification follows closely on compaction, as increased temperatures at depth hasten deposition of cement that binds the grains together. Pressure solution contributes to cementing, as

1200-551: Is observed up to 900 °C (1,650 °F). Although historically there was much disagreement concerning the nature of the metakaolin phase, extensive research has led to a general consensus that metakaolin is not a simple mixture of amorphous silica ( SiO 2 ) and alumina ( Al 2 O 3 ), but rather a complex amorphous structure that retains some longer-range order (but not strictly crystalline ) due to stacking of its hexagonal layers. Further heating to 925–950 °C converts metakaolin to an aluminium-silicon spinel which

1260-597: Is one of the most common minerals; it is mined, as kaolin, in Australia , Brazil , Bulgaria , China , Czech Republic , France , Germany , India , Iran , Malaysia , South Africa , South Korea , Spain , Tanzania , Thailand , United Kingdom , United States and Vietnam . Mantles of kaolinite are common in Western and Northern Europe. The ages of these mantles are Mesozoic to Early Cenozoic. Kaolinite clay occurs in abundance in soils that have formed from

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1320-452: Is reduced. In addition to this physical compaction, chemical compaction may take place via pressure solution . Points of contact between grains are under the greatest strain, and the strained mineral is more soluble than the rest of the grain. As a result, the contact points are dissolved away, allowing the grains to come into closer contact. It is during compaction that shale develops its fissility, likely through mechanical compaction of

1380-465: Is sometimes also referred to as a gamma-alumina type structure: Upon calcination above 1050 °C, the spinel phase nucleates and transforms to platelet mullite and highly crystalline cristobalite : Finally, at 1400 °C the "needle" form of mullite appears, offering substantial increases in structural strength and heat resistance. This is a structural but not chemical transformation. See stoneware for more information on this form. Kaolinite

1440-760: Is surrounded by six oxygen or hydroxyl ions arranged at the corners of an octahedron. The two sheets in each layer are strongly bonded together via shared oxygen ions, while layers are bonded via hydrogen bonding between oxygen on the outer face of the T sheet of one layer and hydroxyl on the outer face of the O sheet of the next layer. A kaolinite layer has no net electrical charge and so there are no large cations (such as calcium, sodium, or potassium) between layers as with most other clay minerals. This accounts for kaolinite's relatively low ion exchange capacity. The close hydrogen bonding between layers also hinders water molecules from infiltrating between layers, accounting for kaolinite's nonswelling character. When moistened,

1500-449: Is that the aluminium cations must be hexacoordinated with respect to oxygen (Caillère and Hénin, 1947; Caillère et al., 1953; Hénin and Robichet, 1955 ). Gastuche et al. (1962) and Caillère and Hénin (1962) have concluded that kaolinite can only ever be formed when the aluminium hydroxide is in the form of gibbsite . Otherwise, the precipitate formed will be a "mixed alumino-silicic gel" (as Millot, 1970, p. 343 put it). If it were

1560-724: The Canadian Rockies foothills in British Columbia , between the Halfway River and Muskwa River . It is composed of silty marine mudstone with fine grained marine sandstone interbeds. Shale Shale is a fine-grained, clastic sedimentary rock formed from mud that is a mix of flakes of clay minerals (hydrous aluminium phyllosilicates, e.g., kaolin , Al 2 Si 2 O 5 ( OH ) 4 ) and tiny fragments ( silt -sized particles) of other minerals, especially quartz and calcite . Shale

1620-570: The Espluga Freda area of Spain were enriched with kaolinite from a detrital source due to denudation . Difficulties are encountered when trying to explain kaolinite formation under atmospheric conditions by extrapolation of thermodynamic data from the more successful high-temperature syntheses. La Iglesia and Van Oosterwijk-Gastuche (1978) thought that the conditions under which kaolinite will nucleate can be deduced from stability diagrams, based as they are on dissolution data. Because of

1680-609: The Newark-Pomeroy line, along which can still be seen many open-pit clay mines. The deposits were formed between the late Cretaceous and early Paleogene , about 100 to 45 million years ago, in sediments derived from weathered igneous and metakaolin rocks. Kaolin production in the United States during 2011 was 5.5 million tons. During the Paleocene–Eocene Thermal Maximum sediments deposited in

1740-399: The U.S. Gulf Coast . As sediments continue to accumulate, the older, more deeply buried sediments begin to undergo diagenesis . This mostly consists of compaction and lithification of the clay and silt particles. Early stages of diagenesis, described as eogenesis , take place at shallow depths (a few tens of meters) and are characterized by bioturbation and mineralogical changes in

1800-416: The silicic acid must be present in concentrations below the maximum solubility of amorphous silica. The principle behind this prerequisite can be found in structural chemistry: "Since the polysilicate ions are not of uniform size, they cannot arrange themselves along with the metal ions into a regular crystal lattice." (Iler, 1955, p. 182 ) The second aspect of the low-temperature synthesis of kaolinite

1860-669: The wave base . Thick deposits of shale are found near ancient continental margins and foreland basins . Some of the most widespread shale formations were deposited by epicontinental seas . Black shales are common in Cretaceous strata on the margins of the Atlantic Ocean , where they were deposited in fault -bounded silled basins associated with the opening of the Atlantic during the breakup of Pangaea . These basins were anoxic, in part because of restricted circulation in

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1920-421: The black coloration. Because amorphous iron sulfide gradually converts to pyrite , which is not an important pigment, young shales may be quite dark from their iron sulfide content, in spite of a modest carbon content (less than 1%), while a black color in an ancient shale indicates a high carbon content. Most shales are marine in origin, and the groundwater in shale formations is often highly saline . There

1980-460: The chemical weathering of rocks in hot, moist climates ; for example in tropical rainforest areas. Comparing soils along a gradient towards progressively cooler or drier climates, the proportion of kaolinite decreases, while the proportion of other clay minerals such as illite (in cooler climates) or smectite (in drier climates) increases. Such climatically related differences in clay mineral content are often used to infer changes in climates in

2040-426: The chemical composition Al 2 Si 2 O 5 ( OH ) 4 . It is a layered silicate mineral , with one tetrahedral sheet of silica ( SiO 4 ) linked through oxygen atoms to one octahedral sheet of alumina ( AlO 6 ). Kaolinite is a soft, earthy, usually white, mineral (dioctahedral phyllosilicate clay ), produced by the chemical weathering of aluminium silicate minerals like feldspar . It has

2100-506: The clumps of clay particles produced by flocculation vary in size from a few tens of microns to over 700 microns in diameter. The floccules start out water-rich, but much of the water is expelled from the floccules as the clay minerals bind more tightly together over time (a process called syneresis ). Clay pelletization by organisms that filter feed is important where flocculation is inhibited. Filter feeders produce an estimated 12 metric tons of clay pellets per square kilometer per year along

2160-408: The color of the rock. Red, brown and green colors are indicative of ferric oxide ( hematite – reds), iron hydroxide ( goethite – browns and limonite – yellow), or micaceous minerals ( chlorite , biotite and illite – greens). The color shifts from reddish to greenish as iron in the oxidized ( ferric ) state is converted to iron in the reduced ( ferrous ) state. Black shale results from

2220-419: The context of underground coal mining , shale was frequently referred to as slate well into the 20th century. Black shale associated with coal seams is called black metal. [REDACTED] Media related to Shale at Wikimedia Commons Kaolinite Kaolinite ( / ˈ k eɪ . ə l ə ˌ n aɪ t , - l ɪ -/ KAY -ə-lə-nyte, -⁠lih- ; also called kaolin ) is a clay mineral , with

2280-413: The daily titrations with hydrochloric acid or sodium hydroxide during at least 60 days will have introduced the necessary element of periodicity. Only now the actual role of what has been described as the "aging" ( Alterung ) of amorphous alumino-silicates (as for example Harder, 1978 had noted) can be fully understood. As such, time is not bringing about any change in a closed system at equilibrium; but

2340-513: The effect of digital media, in 2016 the market share was reported to be: paper, 36%; ceramics, 31%; paint, 7% and other, 26%. According to the USGS , in 2021 the global production of kaolin was estimated to be around 45 million tonnes. Global production of kaolin by country in 2012 was estimated to be: Some selected typical properties of various ceramic grade kaolins are: Kaolin is generally recognized as safe , but may cause mild irritation of

2400-451: The first place the silicic acid to be supplied to the growing crystal must be in a monomeric form, i.e., silica should be present in very dilute solution (Caillère et al., 1957; Caillère and Hénin, 1960; Wey and Siffert, 1962; Millot, 1970 ). In order to prevent the formation of amorphous silica gels precipitating from supersaturated solutions without reacting with the aluminium or magnesium cations to form crystalline silicates ,

2460-608: The geological past, where ancient soils have been buried and preserved. In the Institut National pour l'Étude Agronomique au Congo Belge (INEAC) classification system, soils in which the clay fraction is predominantly kaolinite are called kaolisol (from kaolin and soil). In the United States, the main kaolin deposits are found in central Georgia , on a stretch of the Atlantic Seaboard fall line between Augusta and Macon . This area of thirteen counties

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2520-405: The low-temperature nucleation of kaolinite. At high temperatures, equilibrium thermodynamic models appear to be satisfactory for the description of kaolinite dissolution and nucleation , because the thermal energy suffices to overcome the energy barriers involved in the nucleation process. The importance of syntheses at ambient temperature and atmospheric pressure towards the understanding of

2580-620: The manufacture of Jingdezhen porcelain . D'Entrecolles was transcribing the Chinese term 高嶺土 , now romanized as gāolǐngtǔ in pinyin , taken from the name of the village of Gaoling ("High Ridge") near Ehu in Fuliang County , now part of Jiangxi Province 's Jingdezhen Prefecture . The area around the village had become the main source of Jingdezhen's kaolin over the course of the Qing dynasty . The mineralogical suffix -ite

2640-415: The mechanism involved in the nucleation of clay minerals lies in overcoming these energy barriers. As indicated by Caillère and Hénin (1960) the processes involved will have to be studied in well-defined experiments, because it is virtually impossible to isolate the factors involved by mere deduction from complex natural physico-chemical systems such as the soil environment. Fripiat and Herbillon (1971), in

2700-592: The mineral dissolved from strained contact points is redeposited in the unstrained pore spaces. The clay minerals may be altered as well. For example, smectite is altered to illite at temperatures of about 55 to 200 °C (130 to 390 °F), releasing water in the process. Other alteration reactions include the alteration of smectite to chlorite and of kaolinite to illite at temperatures between 120 and 150 °C (250 and 300 °F). Because of these reactions, illite composes 80% of Precambrian shales, versus about 25% of young shales. Unroofing of buried shale

2760-433: The narrow Atlantic, and in part because the very warm Cretaceous seas lacked the circulation of cold bottom water that oxygenates the deep oceans today. Most clay must be deposited as aggregates and floccules, since the settling rate of individual clay particles is extremely slow. Flocculation is very rapid once the clay encounters highly saline sea water. Whereas individual clay particles are less than 4 microns in size,

2820-441: The only requirement, large amounts of kaolinite could be harvested simply by adding gibbsite powder to a silica solution. Undoubtedly a marked degree of adsorption of the silica in solution by the gibbsite surfaces will take place, but, as stated before, mere adsorption does not create the layer lattice typical of kaolinite crystals. The third aspect is that these two initial components must be incorporated into one mixed crystal with

2880-415: The original open framework of clay particles. The particles become strongly oriented into parallel layers that give the shale its distinctive fabric. Fissility likely develops early in the compaction process, at relatively shallow depth, since fissility does not seem to vary with depth in thick formations. Kaolinite flakes have less tendency to align in parallel layers than other clays, so kaolinite-rich clay

2940-631: The parallel orientation of clay mineral flakes in shale, it breaks into thin layers, often splintery and usually parallel to the otherwise indistinguishable bedding planes . Non-fissile rocks of similar composition and particle size (less than 0.0625 mm) are described as mudstones (1/3 to 2/3 silt particles) or claystones (less than 1/3 silt). Rocks with similar particle sizes but with less clay (greater than 2/3 silt) and therefore grittier are siltstones . Shales are typically gray in color and are composed of clay minerals and quartz grains. The addition of variable amounts of minor constituents alters

3000-418: The plates hydrogen bond directly to each other, so that the dried clay is rigid but still fragile. If the clay is moistened again, it will once more become plastic. Kaolinite group clays undergo a series of phase transformations upon thermal treatment in air at atmospheric pressure. High-energy milling of kaolin results in the formation of a mechanochemically amorphized phase similar to metakaolin , although

3060-817: The presence of greater than one percent carbonaceous material and indicates a reducing environment. Pale blue to blue-green shales typically are rich in carbonate minerals . Clays are the major constituent of shales and other mudrocks. The clay minerals represented are largely kaolinite , montmorillonite and illite. Clay minerals of Late Tertiary mudstones are expandable smectites , whereas in older rocks (especially in mid-to early Paleozoic shales) illites predominate. The transformation of smectite to illite produces silica , sodium , calcium , magnesium , iron and water. These released elements form authigenic quartz , chert , calcite , dolomite , ankerite , hematite and albite , all trace to minor (except quartz) minerals found in shales and other mudrocks. A typical shale

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3120-432: The properties of this solid are quite different. The high-energy milling process is highly inefficient and consumes a large amount of energy. Below 100 °C, exposure to low humidity air will result in the slow evaporation of any liquid water in the kaolin. At low moisture content the mass can be described leather dry , and at near 0% moisture it is referred to as bone dry . Above 100 °C any remaining free water

3180-444: The richest source rocks may contain as much as 40% organic matter. The organic matter in shale is converted over time from the original proteins, polysaccharides , lipids , and other organic molecules to kerogen , which at the higher temperatures found at greater depths of burial is further converted to graphite and petroleum. Before the mid-19th century, the terms slate , shale and schist were not sharply distinguished. In

3240-413: The role of periodicity becomes convincingly clear. DeKimpe et al. (1961) had used daily additions of alumina (as AlCl 3 ·6 H 2 O ) and silica (in the form of ethyl silicate ) during at least two months. In addition, adjustments of the pH took place every day by way of adding either hydrochloric acid or sodium hydroxide . Such daily additions of Si and Al to the solution in combination with

3300-433: The sediments, with only slight compaction. Pyrite may be formed in anoxic mud at this stage of diagenesis. Deeper burial is accompanied by mesogenesis , during which most of the compaction and lithification takes place. As the sediments come under increasing pressure from overlying sediments, sediment grains move into more compact arrangements, ductile grains (such as clay mineral grains) are deformed, and pore space

3360-580: The skin or mucous membranes. Kaolin products may also contain traces of crystalline silica , a known carcinogen if inhaled. In the US, the Occupational Safety and Health Administration (OSHA) has set the legal limit ( permissible exposure limit ) for kaolin exposure in the workplace as 15 mg/m total exposure and 5 mg/m respiratory exposure over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has set

3420-421: The tiny platelike crystals of kaolinite acquire a layer of water molecules that cause crystals to adhere to each other and give kaolin clay its cohesiveness. The bonds are weak enough to allow the plates to slip past each other when the clay is being molded, but strong enough to hold the plates in place and allow the molded clay to retain its shape. When the clay is dried, most of the water molecules are removed, and

3480-864: The transition of allophane into kaolinite has been stressed by Tamura and Jackson (1953). The role of alternations between wetting and drying on the formation of kaolinite has also been noted by Moore (1964). Syntheses of kaolinite at high temperatures (more than 100 °C [212 °F]) are relatively well known. There are for example the syntheses of Van Nieuwenberg and Pieters (1929); Noll (1934); Noll (1936); Norton (1939); Roy and Osborn (1954); Roy (1961); Hawkins and Roy (1962); Tomura et al. (1985); Satokawa et al. (1994) and Huertas et al. (1999). Relatively few low-temperature syntheses have become known (cf. Brindley and DeKimpe (1961); DeKimpe (1969); Bogatyrev et al. (1997) ). Laboratory syntheses of kaolinite at room temperature and atmospheric pressure have been described by DeKimpe et al. (1961). From those tests

3540-414: The waters and destroyed organic matter before it could accumulate. The absence of carbonate rock in shale beds reflects the absence of organisms that might have secreted carbonate skeletons, also likely due to an anoxic environment. As a result, about 95% of organic matter in sedimentary rocks is found in shales and other mudrocks. Individual shale beds typically have an organic matter content of about 1%, but

3600-400: Was later added to generalize the name to cover nearly identical minerals from other locations. Kaolinite is also occasionally discussed under the archaic names lithomarge and lithomarga from Latin lithomarga , a combination of litho- ( ‹See Tfd› Greek : λίθος ， líthos , "stone") and marga (" marl "). In more proper modern use, lithomarge now refers specifically to

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