The Kaolin deposits of the Charentes Basin in France are

clay Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4). Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...

deposits formed

sediment Sediment is a naturally occurring material that is broken down by processes of weathering and erosion, and is subsequently transported by the action of wind, water, or ice or by the force of gravity acting on the particles. For example, sand an ...

arily and then confined by other geological structures.

Overview

The geological unit called Charentes basin is composed of

Eocene The Eocene ( ) Epoch is a geological epoch (geology), epoch that lasted from about 56 to 33.9 million years ago (mya). It is the second epoch of the Paleogene Period (geology), Period in the modern Cenozoic Era (geology), Era. The name ''Eocene' ...

and

Oligocene The Oligocene ( ) is a geologic epoch of the Paleogene Period and extends from about 33.9 million to 23 million years before the present ( to ). As with other older geologic periods, the rock beds that define the epoch are well identified but the ...

deposits, laid above

karst Karst is a topography formed from the dissolution of soluble rocks such as limestone, dolomite, and gypsum. It is characterized by underground drainage systems with sinkholes and caves. It has also been documented for more weathering-resistant ro ...

limestone Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of . Limestone forms whe ...

formations of the

Campanian The Campanian is the fifth of six ages of the Late Cretaceous Epoch on the geologic timescale of the International Commission on Stratigraphy (ICS). In chronostratigraphy, it is the fifth of six stages in the Upper Cretaceous Series. Campanian s ...

, in the north of the

Aquitaine Basin The Aquitaine Basin is the second largest Mesozoic and Cenozoic sedimentary basin in France after the Paris Basin, occupying a large part of the country's southwestern quadrant. Its surface area covers 66,000 km2 onshore. It formed on Varisca ...

. The Charentes basin is named after the departments of

Charente Charente (; Saintongese: ''Chérente''; oc, Charanta ) is a department in the administrative region of Nouvelle-Aquitaine, south western France. It is named after the river Charente, the most important and longest river in the department, an ...

and

Charente-Maritime Charente-Maritime () is a department in the Nouvelle-Aquitaine region on the southwestern coast of France. Named after the river Charente, its prefecture is La Rochelle. As of 2019, it had a population of 651,358 with an area of 6,864 square kil ...

. The

kaolin Kaolinite ( ) is a clay mineral, with the chemical composition Al2 Si2 O5( OH)4. It is an important industrial mineral. It is a layered silicate mineral, with one tetrahedral sheet of silica () linked through oxygen atoms to one octahedral ...

clays of Charentes belong to this mainly continental formation often referred as ''siderolithic'', of which the principal outcrop is situated in the South of the Charente-Maritime department, going north-east from Bordeaux city. The quarries are scattered along a long, wide, north - south band. The clay concentrations of economic value are composed of a succession of clays, sands and pebbles. This torrential-stream deposit, close to enlaced rivers, laid to the deposition of sandy-clayey materials, with a variable iron content, coming from a

lateritic Laterite is both a soil and a rock type rich in iron and aluminium and is commonly considered to have formed in hot and wet tropical areas. Nearly all laterites are of rusty-red coloration, because of high iron oxide content. They develop by ...

weathering Weathering is the deterioration of rocks, soils and minerals as well as wood and artificial materials through contact with water, atmospheric gases, and biological organisms. Weathering occurs ''in situ'' (on site, with little or no movement), ...

, of the French “

Massif Central The (; oc, Massís Central, ; literally ''"Central Massif"'') is a highland region in south-central France, consisting of mountains and plateaus. It covers about 15% of mainland France. Subject to volcanism that has subsided in the last 10,0 ...

”

granite Granite () is a coarse-grained ( phaneritic) intrusive igneous rock composed mostly of quartz, alkali feldspar, and plagioclase. It forms from magma with a high content of silica and alkali metal oxides that slowly cools and solidifies under ...

s. The presence of numerous lignite rich levels indicates that the deposit was performed in the presence of abundant organic matter, leading to important pedogenetic and

diagenetic Diagenesis () is the process that describes physical and chemical changes in sediments first caused by water-rock interactions, microbial activity, and compaction after their deposition. Increased pressure and temperature only start to play a ...

possibilities of evolutions. These chemical and mineralogical evolutions (dissolution–crystallization) allow the neo-formation of kaolin and

gibbsite Gibbsite, Al(OH)3, is one of the mineral forms of aluminium hydroxide. It is often designated as γ-Al(OH)3 (but sometimes as α-Al(OH)3.). It is also sometimes called hydrargillite (or hydrargyllite). Gibbsite is an important ore of aluminiu ...

, as well as

iron sulfide Iron sulfide or Iron sulphide can refer to range of chemical compounds composed of iron and sulfur. Minerals By increasing order of stability: * Iron(II) sulfide, FeS * Greigite, Fe3S4 (cubic) * Pyrrhotite, Fe1−xS (where x = 0 to 0.2) (monocli ...

. At their basement, highly enlaced and with channel shapes, those deposits often fill karstic depressions, leading to the formation of ''clay wells''. The juxtaposition of features are sometimes without explanations using the deposition laws, probably in relation with post-sedimentary strain phenomena, eventually linked to substratum collapse. In the upper part of the series, the deposits are more regular, with lateral extensions up to several hundreds of meters. Those complex geometries, with structures smaller than 20 meters, lead to particularly difficult recognition, estimation and exploitation phases. To this complex geometry, one should notice important lithology variations. The AGS company uses no less than 24 description codes and 8 colour codes, for its samples description. Those classes are subdivided to take into account the grade in

organic matter Organic matter, organic material, or natural organic matter refers to the large source of carbon-based compounds found within natural and engineered, terrestrial, and aquatic environments. It is matter composed of organic compounds that have c ...

iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...

titanium Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...

potassium Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosphe ...

, the colour, and the aptitude to flow.

Geometry of the retaining structures

The uncertainty in estimating the tonnage of mineral resources or ore reserves depends on a number of factors, and the uncertainty of definition of the deposit boundaries is one of them. In deposits with sharp contacts, the geometry may be relatively simple, nevertheless, there is always uncertainty caused by lack of information and large drill hole grid. Generally, these boundaries are determined by mineral grade rather than geological properties: deposit boundaries are chosen based on the cut-off grade. Changing the important factor of cut-off grade, the boundaries of the deposit can be extended or contracted. For this reason, even for the deposits with sharp boundaries, a clear definition of the cut-off grade and distinction between ore and

gangue In mining, gangue () is the commercially worthless material that surrounds, or is closely mixed with, a wanted mineral in an ore deposit. It is thus distinct from overburden, which is the waste rock or materials overlying an ore or mineral body ...

due to dilution during mining, the presence of intermediate layer and the limitation of mining in a selective way are essential. However, in the case of the exploitation of soft materials, extraction can be done more selectively and it would be easier to take into account the geological and geometrical limits. On the other hand, sometimes the uncertainty on the estimation of grades is bigger than the uncertainty on the boundaries definition. Estimation is then performed inside predefined boundaries. One can imagine that the anisotropy and structural complexity of the deposit are due to its geometrical form, while the geometrical dimension of the deposit help us to guess about its economical value. Geometrical features can appear in variographic studies and usually they affect, or hide, grade distribution structures. The presence of a series of nearly homogeneous kaolin areas, linked together in ''zones'', creates a mosaic effect. This phenomenon is due to the existence of periodical settling regimes of the rivers. The size of these ''zones'' can affect the form of the

variogram In spatial statistics the theoretical variogram 2\gamma(\mathbf_1,\mathbf_2) is a function describing the degree of spatial dependence of a spatial random field or stochastic process Z(\mathbf). The semivariogram \gamma(\mathbf_1,\mathbf_2) is ...

and increase the nugget effect due to high differences of values in the edge of the ''zones''. A hole effect is one of the other known phenomena caused by the presence of two or more separated lenses with low difference in grade and shape. The distance between these lenses can thus be estimated.

Transformation during and after sedimentation

Thiry has mentioned that the actual geological setting of kaolin depositions cannot be explained with only transportation and sedimentation cycles. He also stated that the mineralogical sequences cannot be interpreted without local geochemical transformations. Kulbicki has proved the existence of vermicular minerals (kaolinite and

dickite Dickite () is a phyllosilicate clay mineral named after the metallurgical chemist Allan Brugh Dick, who first described it. It is chemically composed of 20.90% aluminium, 21.76% silicon, 1.56% hydrogen and 55.78% oxygen. It has the same comp ...

) incompatible with normal sedimentary sequences.

Influence of the organic materials

Lignite formations are relatively frequent in Charentes clay deposits. Their thickness changes between some decimeters in lenses, to metric scale in continuous forms. These organic materials had some influences on kaolin deposited layers. Some of the observed influences are as follow: In gathered samples close to these organic materials, clays generally do not contain mica minerals, and especially in the neighborhood of Cuisian lignite, kaolinite is very well-ordered and the clay does not contain swelling clays with hydrazine. Occurrence of

is always associated with these well-ordered kaolinites. Normally occurrence of hyper-aluminous clays due to the existence of gibbsite is one of the interesting subjects in the history of these kaolins. This causes many discussions about the origin of this mineral. The existence of gibbsite has been mentioned in the studies of Languine and Halm (1951), Caillere and Jourdain (1956), Kulbickie (1956), Dubreuilh et al. (1984) and Delineau (1994).

Sandy overburden and intermediate sands

Generally, kaolin deposits have been covered with colored sequences of sand. In some quarries, we can observe red, green and some times black sands. The black color might be due to the existence of

pyrite The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Iron, FeSulfur, S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral. Pyrite's metallic Luster (mineralogy), lust ...

and organic materials. Sometimes fossil woods (floated branches and trunks of trees) can be found and with the coarse size of pebbles (several millimeters) are evidence of a high energy transportation. This type of sand can have some influences on the leaching by mineral and organic acids produced by pyrite and organic materials, of the lower kaolin deposits. Thiry has found that generally these kaolins contain rather well-ordered kaolinite. Obviously, the level of crystallization can control technical properties of kaolinite as well as the structural impurities. The high energy current can interrupt the continuity of the settled layers of kaolin and reduce the simplicity of the estimation methods.

Gibbsite

Gibbsite is not stable in presence of quartz and it will be changed into kaolinite minerals, so gibbsite has formed after the deposition and we can call it neo-formation gibbsite. Now, the main question is about gibbsite formation in the middle of kaolin series. Due to the pH of leaching, a dissolution of Al₂O₃ or SiO₂ can occur (podzol or laterite profile) The first theory tries to describe this with podzol profiles: it assumes the leaching of silica from minerals and accordingly the gibbsite formation from leached kaolin. We thus should find the hyper-aluminous materials, containing gibbsite in the lower series of kaolin. On the other hand, a second theory proposes the procedure of aluminium leaching in a very acid medium, in deposited organic materials (lignite) with clay. The organic materials can accelerate the solubilization and transportation of aluminium ions with intervention of organic complex.Thiry, 1984 proposed the following scenarios for this dissolved aluminium. Dissolved aluminium can be transported with complex to a less acidic medium. :1- if there is any quartz in this medium, it can react, and we obtain well-ordered kaolinite minerals :2- In absence of quartz, aluminium will precipitate as a hydroxide mineral: gibbsite. This theory alone cannot explain what is observed in-situ in the some samples of the “BD” deposit, where gibbsite was found in sandy layers containing quartz.

References

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