CLAY (from O. Eng. claeg, a word common in various forms to Teutonic languages, cf. Ger. Klei), commonly defined as a fine-grained, almost impalpable substance, very soft, more or less coherent when dry, plastic and retentive of water when wet; it has an “earthy” odour when breathed upon or moistened, and consists essentially of hydrous aluminium silicate with various impurities. Of clay are formed a great number of rocks, which collectively are known as “clay-rocks” or “pelitic rocks” (from Gr. πηλός, clay), e.g. mudstone, shale, slate: these exhibit in greater or less perfection the properties above described according to their freedom from impurities. In nature, clays are rarely free from foreign ingredients, many of which can be detected with the unaided eye, while others may be observed by means of the microscope. The commonest impurities are:— (1) organic matter, humus, &c. (exemplified by clay-soils with an admixture of peat, oil shales, carbonaceous shales); (2) fossils (such as plants in the shales of the Lias and Coal Measures, shells in clays of all geological periods and in fresh water marls); (3) carbonate of lime (rarely altogether absent, but abundant in marls, cement-stones and argillaceous limestones); (4) sulphide of iron, as pyrite or marcasite (when finely diffused, giving the clay a dark grey-blue colour, which weathers to brown—e.g. London Clay; also as nodules and concretions, e.g. Gault); (5) oxides of iron (staining the clay bright red when ferric oxide, red ochre; yellow when hydrous, e.g. yellow ochre); (6) sand or detrital silica (forming loams, arenaceous clays, argillaceous sandstones, &c.). Less frequently present are the following:—rock salt (Triassic clays, and marls of Cheshire, &c.); gypsum (London Clay, Triassic clays); dolomite, phosphate of lime, vivianite (phosphate of iron), oxides of manganese, copper ores (e.g. Kupferschiefer), wavellite and amber. As the impurities increase in amount the clay rocks pass gradually into argillaceous sands and sandstones, argillaceous limestones and dolomites, shaly coals and clay ironstones.
Natural clays, even when most pure, show a considerable range of composition, and hence cannot be regarded as consisting of a single mineral; clay is a rock, and has that variability which characterizes all rocks. Of the essential properties of clay some are merely physical, and depend on the minute size of the particles. If any rock be taken (even a piece of pure quartz) and crushed to a very fine powder, it will show some of the peculiarities of clays; for example, it will be plastic, retentive of moisture, impermeable to water, and will shrink to some extent if the moist mass be kneaded, and then allowed to dry. It happens, however, that many rocks are not disintegrated to this extreme degree by natural processes, and weathering invariably accompanies disintegration. Quartz, for example, has little or no cleavage, and is not attacked by the atmosphere. It breaks up into fragments, which become rounded by attrition, but after they reach a certain minuteness are borne along by currents of water or air in a state of suspension, and are not further reduced in size. Hence sands are more coarse grained than clays. A great number of rock-forming minerals, however, possess a good cleavage, so that when bruised they split into thin fragments; many of these minerals decompose somewhat readily, yielding secondary minerals, which are comparatively soft and have a scaly character, with eminently perfect cleavages, which facilitate splitting into exceedingly thin plates. The principal substances of this description are kaolin, muscovite and chlorite. Kaolin and muscovite are formed principally after felspar (and the felspars are the commonest minerals of all crystalline rocks); also from nepheline, leucite, scapolite and a variety of other rock-forming minerals. Chlorite arises from biotite, augite and hornblende. Serpentine, which may be fibrous or scaly, is a secondary product of olivine and certain pyroxenes. Clays consist essentially of the above ingredients (although serpentine is not known to take part in them to any extent, it is closely allied to chlorite). At the same time other substances are produced as decomposition goes on. They are principally finely divided quartz, epidote, zoisite, rutile, limonite, calcite, pyrites, and very small particles of these are rarely absent from natural clays. These fine-grained materials are at first mixed with broken and more or less weathered rock fragments and coarser mineral particles in the soil and subsoil, but by the action of wind and rain they are swept away and deposited in distant situations. “Loess” is a fine calcareous clay, which has been wind-borne, and subsequently laid down on the margins of dry steppes and deserts. Most clays are water-borne, having been carried from the surface of the land by 473 rain and transported by the brooks and rivers into lakes or the sea. In this state the fine particles are known as “mud.” They are deposited where the currents are checked and the water becomes very still. If temporarily laid down in other situations they are ultimately lifted again and removed. A little clay, stirred up with water in a glass vessel, takes hours to settle, and even after two or three days some remains in suspension; in fact, it has been suggested that in such cases the clay forms a sort of “colloidal solution” in the water. Traces of dissolved salts, such as common salt, gypsum or alum, greatly accelerate deposition. For these reasons the principal gathering places of fine pure clays are deep, still lakes, and the sea bottom at considerable distances from the shore. The coarser materials settle nearer the land, and the shallower portions of the sea floor are strewn with gravel and sand, except in occasional depressions and near the mouths of rivers where mud may gather. Farther out the great mud deposits begin, extending from 50 to 200 m. from the land, according to the amount of sediment brought in, and the rate at which the water deepens. A girdle of mud accumulations encircles all the continents. These sediments are fine and tenacious; their principal components, in addition to clay, being small grains of quartz, zircon, tourmaline, hornblende, felspar and iron compounds. Their typical colour is blackish-blue, owing to the abundance of sulphuretted hydrogen; when fresh they have a sulphurous odour, when weathered they are brown, as their iron is present as hydrous oxides (limonite, &c). These deposits are tenanted by numerous forms of marine life, and the sulphur they contain is derived from decomposing organic matter. Occasionally water-logged plant débris is mingled with the mud. In a few places a red colour prevails, the iron being mostly oxidized; elsewhere the muds are green owing to abundant glauconite. Traced landwards the muds become more sandy, while on their outer margins they grade into the abysmal deposits, such as the globigerina ooze (see Ocean and Oceanography). Near volcanoes they contain many volcanic minerals, and around coral islands they are often in large part calcareous.
Microscopic sections of some of the more coherent clays and shales may be prepared by saturating them with Canada balsam by long boiling, and slicing the resultant mass in the same manner as one of the harder rocks. They show that clay rocks contain abundant very small grains of quartz (about 0.01 to 0.05 mm. in diameter), with often felspar, tourmaline, zircon, epidote, rutile and more or less calcite. These may form more than one-third of an ordinary shale; the greater part, however, consists of still smaller scales of other minerals (0.01 mm. in diameter and less than this). Some of these are recognizable as pale yellowish and white mica; others seem to be chlorite, the remainder is perhaps kaolin, but, owing to the minute size of the flakes, they yield very indistinct reactions to polarized light. They are also often stained with iron oxide and organic substances, and in consequence their true nature is almost impossible to determine. It is certain, however, that the finer-grained rocks are richest in alumina, and in combined water; hence the inference is clear that kaolin or some other hydrous aluminium silicate is the dominating constituent. These results are confirmed by the mechanical analysis of clays. This process consists in finely pulverizing the soil or rock, and levigating it in vessels of water. A series of powders is obtained progressively finer according to the time required to settle to the bottom of the vessel. The clay is held to include those particles which have less than 0.005 mm. diameter, and contains a higher percentage of alumina than any of the other ingredients.
As might be inferred from the differences they exhibit in other respects, clay rocks vary greatly in their chemical composition. Some of them contain much iron (yellow, blue and red clays); others contain abundant calcium carbonate (calcareous clays and marls). Pure clays, however, may be found almost quite free from these substances. Their silica ranges from about 60 to 45%, varying in accordance with the amount of quartz and alkali-felspar present. It is almost always more than would be the case if the rock consisted of kaolin mixed with muscovite. Alumina is high in the finer clays (18 to 30%), and they are the most aluminous of all sediments, except bauxite. Magnesia is never absent, though its amount may be less than 1%; it is usually contained in minerals of the chlorite group, but partly also in dolomite. The alkalis are very interesting; often they form 5 or 10% of the whole rock; they indicate abundance of white micas or of undecomposed particles of felspar. Some clays, however, such as fireclays, contain very little potash or soda, while they are rich in alumina; and it is a fair inference that hydrated aluminous silicates, such as kaolin, are well represented in these rocks. There are, in fact, a few clays which contain about 45% of alumina, that is to say, more than in pure kaolin. It is probable that these are related to bauxite and certain kinds of laterite.
A few of the most important clay rocks, such as china-clay, brick-clay, red-clay and shale, may be briefly described here.
China-clay is white, friable and earthy. It occurs in regions of granite, porphyry and syenite, and usually occupies funnel-shaped cavities of no great superficial area, but of considerable depth. It consists of very fine scaly kaolin, larger, shining plates of white mica, grains of quartz and particles of semi-decomposed felspar, tourmaline, zircon and other minerals, which originally formed part of the granite. These clays are produced by the decomposition of the granite by acid vapours, which are discharged after the igneous rock has solidified (“fumarole or pneumatolytic action”). Fluorine and its compounds are often supposed to have been among the agencies which produce this change, but more probably carbonic acid played the principal role. The felspar decomposes into kaolin and quartz; its alkalis are for the most part set free and removed in solution, but are partly retained in the white mica which is constantly found in crude china-clays. Semi-decomposed varieties of the granite are known as china-stone. The kaolin may be washed away from its original site, and deposited in hollows or lakes to form beds of white clay, such as pipe-clay; in this case it is always more or less impure. Yellow and pinkish varieties of china-clay and pipe-clay contain a small quantity of oxide of iron. The best known localities for china-clay are Cornwall, Limoges (France), Saxony, Bohemia and China; it is found also in Pennsylvania, N. Carolina and elsewhere in the United States.
Fire-clays include all those varieties of clay which are very refractory to heat. They must contain little alkalis, lime, magnesia and iron, but some of them are comparatively rich in silica. Many of the clays which pass under this designation belong to the Carboniferous period, and are found underlying seams of coal. Either by rapid growth of vegetation, or by subsequent percolation of organic solutions, most of the alkalis and the lime have been carried away.
Any argillaceous material, which can be used for the manufacture of bricks, may be called a brick-clay. In England, Kimmeridge Clay, Lias clays, London Clay and pulverized shale and slate are all employed for this purpose. Each variety needs special treatment according to its properties. The true brick-clays, however, are superficial deposits of Pleistocene or Quaternary age, and occur in hollows, filled-up lakes and deserted stream channels. Many of them are derived from the glacial boulder-clays, or from the washing away of the finer materials contained in older clay formations. They are always very impure.
The red-clay is an abysmal formation, occurring in the sea bottom in the deepest part of the oceans. It is estimated to cover over fifty millions of square miles, and is probably the most extensive deposit which is in course of accumulation at the present day. In addition to the reddish or brownish argillaceous matrix it contains fresh or decomposed crystals of volcanic minerals, such as felspar, augite, hornblende, olivine and pumiceous or palagonitic rocks. These must either have been ejected by submarine volcanoes or drifted by the wind from active vents, as the fine ash discharged by Krakatoa was wafted over the whole globe. Larger rounded lumps of pumice, found in the clay, have probably floated to their present situations, and sank when decomposed, all their cavities becoming filled 474 with sea water. Crystals of zeolites (phillipsite) form in the red-clay as radiate, nodular groups. Lumps of manganese oxide, with a black, shining outer surface, are also characteristic of this deposit, and frequently encrust pieces of pumice or animal remains. The only fossils of the clay are radiolaria, sharks’ teeth and the ear-bones of whales, precisely those parts of the skeleton of marine creatures which are hardest and can longest survive exposure to sea-water. Their comparative abundance shows how slowly the clay gathers. Small rounded spherules of iron, believed by some to be meteoric dust, have also been obtained in some numbers. Among the rocks of the continents nothing exactly the same as this remarkable deposit is known to occur, though fine dark clays, with manganese nodules, are found in many localities, accompanied by other rocks which indicate deep-water conditions of deposit.
Another type of red-clay is found in caves, and is known as cave-earth or red-earth (terra rossa). It is fine, tenacious and bright red, and represents the insoluble and thoroughly weathered impurities which are left behind when the calcareous matter is removed in solution by carbonated waters. Similar residual clays sometimes occur on the surface of areas of limestone in hollows and fissures formed by weathering.
Boulder-clay is a coarse unstratified deposit of fine clay, with more or less sand, and boulders of various sizes, the latter usually marked with glacial striations.
Some clay rocks which have been laid down by water are very uniform through their whole thickness, and are called mud-stones. Others split readily into fine leaflets or laminae parallel to their bedding, and this structure is accentuated by the presence of films of other materials, such as sand or vegetable debris. Laminated clays of this sort are generally known as shales; they occur in many formations but are very common in the Carboniferous. Some of them contain much organic debris, and when distilled yield paraffin oil, wax, compounds of ammonia, &c. In these oil-shales there are clear, globular, yellow bodies which seem to be resinous. It has been suggested that the admixture of large quantities of decomposed fresh-water algae among the original mud is the origin of the paraffins. In New South Wales, Scotland and several parts of America such oil-shales are worked on a commercial scale. Many shales contain great numbers of ovoid or rounded septarian nodules of clay ironstone. Others are rich in pyrites, which, on oxidation, produces sulphuric acid; this attacks the aluminous silicates of the clay and forms aluminium sulphate (alum shales). The lias shales of Whitby contain blocks of semi-mineralized wood, or jet, which is black with a resinous lustre, and a fibrous structure. The laminated structure of shales, though partly due to successive very thin sheets of deposit, is certainly dependent also on the vertical pressure exerted by masses of super-incumbent rock; it indicates a transition to the fissile character of clay slates.(J. S. F.)
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