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ECONOMIC FEATURES
There are several sources of nitrogen for fertilizer purposes: mineral nitrates, nitrogen taken from the air by certain plants with the aid of bacteria and plowed into the soil, nitrogen taken directly from the air by combining nitrogen and oxygen atoms in an electric arc, or by combining nitrogen and hydrogen to form ammonia, nitrogen taken from the air to make a compound of calcium, carbon, and nitrogen (cyanamid), nitrogen saved from coal in the form of ammonia as a by-product of c.o.ke-manufacture, and nitrogen from various organic wastes. Nitrogen in the form of ammonia is also one of the potential products of oil-shales (p. 150). While the princ.i.p.al use of nitrogenous materials is as fertilizers, additional important quant.i.ties are used in ammonia for refrigerating plants, and in the form of nitric acid in a large number of chemical industries. During the war the use of nitrates was largely diverted to explosives manufacture. The geologist is interested princ.i.p.ally in the mineral nitrates as a mineral resource, but the other sources of nitrogen, particularly its recovery from coal, also touch his field.
Almost the single source of mineral nitrates for the world at present is Chile, where there are deposits of sodium nitrate or Chile saltpeter, containing minor amounts of pota.s.sium nitrate. About two-thirds of the Chilean material normally goes to Europe and about one-fourth to the United States. The supply has been commercially controlled chiefly by Great Britain and by Chilean companies backed by British and German capital.
The dependence of the world on Chile became painfully apparent during the war. Germany was the only nation which had developed other sources of nitrogenous material to any great extent. The other nations were dependent in a very large degree on the mineral nitrates, both for fertilizer and munition purposes. Total demands far exceeded the total output from Chile, requiring international agreement as to the division of the output among the nations. The stream of several hundred ships carrying nitrates from Chile was one of the vital war arteries. This situation led to strenuous efforts in the belligerent countries toward the development of other sources of nitrogen. The United States, under governmental appropriation, began the building of extensive plants for the fixation of nitrogen from the air, and the building of by-product c.o.ke ovens in the place of the old wasteful beehive ovens was accelerated. Germany before the war had already gone far in both of these directions, not only within her own boundaries, but in the building of fixation plants in Scandinavia and Switzerland. War conditions required further development of these processes in Germany, with the result that this country was soon entirely self-supporting in this regard. One of the effects was the almost complete elimination in Germany of anything but the by-product process of c.o.king coal.
War-time development of the nitrogen industry in the United States for munition purposes brought the domestic production almost up to the pre-war requirements for fertilizers alone. With the increasing demand for fertilizers and with the cheapness of the Chilean supply of natural nitrates, it is likely that the United States will continue for a good many years to import considerable amounts of Chilean nitrates. It may be noted that, although this country normally consumes about one-fourth of the Chilean product, American interests commercially control less than one-twentieth of the output. Presumably, if for no other purpose than future protection, effort will be made to develop the domestic industry to a point where in a crisis the United States could be independent of Chile. Particularly may an increase in the output of by-product ammonia from c.o.ke manufacture be looked for (see also pp. 118-119), since nitrogenous material thus produced need bear no fixed part of the cost of production, and requires no protective tariff.
The reserves of Chilean nitrate are known to be sufficient for world requirements for an indefinitely long future.
GEOLOGIC FEATURES
Mineral nitrates in general, and particularly those of soda and potash, are readily soluble at ordinary temperatures. Mineral nitrate deposits are therefore very rare, and are found only in arid regions or other places where they are protected from rain and ground-water. The only large deposits known are those of northern Chile and some extensions in adjacent parts of Peru and Bolivia. These are located on high desert plateaus, where there is almost a total absence of rain, and form blankets of one to six feet in thickness near the surface. The most important mineral, the sodium nitrate or Chile saltpeter, is mingled with various other soluble salts, including common salt, borax minerals, and pota.s.sium nitrate, and with loose clay, sand, and gravel. The nitrate deposits occur largely around and just above slight basin-like depressions in the desert which contain an abundance of common salt. The highest grade material contains 40 to 50 per cent of sodium nitrate, and material to be of shipping grade must run at least 12 to 15 per cent.
The origin of the nitrate beds is commonly believed to be similar to that of beds of rock salt (pp. 295-298), borax, and other saline residues. The source of the nitrogen was probably organic matter in the soil, such as former deposits of bird guano, bones (which are actually found in the same desert basin), and ancient vegetable matter. By the action of nitrifying bacteria on this organic matter, nitrate salts are believed to have formed which were leached out by surface and ground waters, and probably carried in solution to enclosed bodies of water.
Here they became mingled with various other salts, and all were precipitated out as the waters of the basins evaporated. Deliquescence and later migration of the more soluble nitrates resulted in their acc.u.mulation around the edges of the basins. The nitrate beds are thus essentially a product of desiccation.
While the origin just set forth is rather generally accepted, several other theories have been advanced. It has been suggested that the deposits were not formed in water basins, but that ground water carrying nitrates in solution has been and is rising to the surface,--where, under the extremely arid conditions, it evaporates rapidly, leaving the nitrates mixed with the surface clays. One group of writers accounts for the deposits by the fixation of atmospheric nitrogen through electrical phenomena. Still others note the frequent presence of nitrogen in volcanic exhalations and the a.s.sociation of the Chilean nitrate beds with surface volcanic rocks; they suggest that these rocks were the source of the nitrogen, which under unusual climatic conditions was leached out and then deposited by evaporation.
PHOSPHATES
ECONOMIC FEATURES
The princ.i.p.al use of natural phosphates is in the manufacture of fertilizers. They are also used in the manufacture of phosphorus, phosphoric acid, and other phosphorus compounds, for matches, for certain metallurgical operations, and for gases used in military operations.
The material mined is mainly a phosphate of lime (tricalcium phosphate).
To make it available for plant use, it is treated with sulphuric acid to form a soluble superphosphate; hence the importance of sulphuric acid, and its mineral sources pyrite and sulphur, in the fertilizer industry.
A small percentage of the phosphate is also ground up and applied directly to the soil in the raw form. Other phosphatic materials are the basic slag from phosphatic iron ores made into Thomas-process steel, guano from the Pacific islands, and bone and refuse (tankage) from the cattle raising and packing countries. These materials are used for the same purposes as the natural phosphates.
The United States is the largest factor in the world's phosphate industry, with reference both to production and reserves.
The largest and most available of the European sources are in Tunis and Algeria, under French control, and in Egypt, under English control.
Belgium and northern France have been considerable producers of phosphates, but, with the development of higher grade deposits in other countries, their production has fallen to a very small fraction of the world's total. There also has been very small and insignificant production in Spain and Great Britain. Russia has large reserves which are practically unmined.
While there is comparatively little phosphate rock in western Europe, a considerable amount of the phosphate supply is obtained as a by-product from Thomas slag, derived from phosphatic iron ores. These ores are chiefly from Lorraine and Sweden, but English and Russian ores can be similarly used.
Outside of Europe and the United States, there are smaller phosphate supplies in Canada, the Dutch West Indies, Venezuela, Chile, South Australia, New Zealand, and several islands of the Indian and South Pacific Oceans. None of these has yet contributed largely to world production, and their distance from the princ.i.p.al consuming countries bordering the North Atlantic basin is so great that there is not likely to be any great movement to this part of the world. On the other hand, some of the South Sea islands have large reserves of exceptionally high grade guano and bone phosphates, which will doubtless be used in increasing amounts for export to j.a.pan, New Zealand, and other nearby countries. The most important of these islands are now controlled by Great Britain, j.a.pan, and France.
A striking feature of the situation is that the central European countries, which have been large consumers of phosphate material, have lost not only the Pacific island phosphates but the Lorraine phosphatic iron ores, and are now almost completely dependent on British, French, and United States phosphate.
In the United States, reserves of phosphate are very large. They are mined princ.i.p.ally in Florida, Tennessee, and South Carolina; but great reserves, though of lower grade, are known in Arkansas, Montana, Idaho, Wyoming, and Utah. There are possibilities for the development of local phosphate industries in the west, in connection with the manufacture of sulphuric acid from waste smelting gases at nearby mining centers. The Anaconda Copper Mining Company has taken up the manufacture of superphosphate as a means of using sulphuric acid made in relation to its smelting operations. The United States is independent in phosphate supplies and has a surplus for export. This country, England, and France exercise control of the greater part of the world's supply of phosphatic material. In compet.i.tion for world trade, the Florida and Carolina phosphates are favorably situated for export, but there is strong compet.i.tion in Europe from the immense fields in French North Africa, which are about equally well situated.
GEOLOGIC FEATURES
Small amounts of phosphorus are common in igneous rocks, in the form of the mineral apat.i.te (calcium phosphate with calcium chloride or fluoride). Apat.i.te is especially abundant in some pegmat.i.tes. In a few places, as in the Adirondacks where magnetic concentration of iron ores leaves a residue containing much apat.i.te, and in Canada and Spain where veins of apat.i.te have been mined, this material is used as a source of phosphate fertilizer. The great bulk of the world's phosphate, however, is obtained from other sources--sedimentary and residual beds described below.
Phosphorus in the rocks is dissolved in one form or another by the ground-waters; a part of it is taken up by land plants and animals for the building of their tissues, and another part goes in solution to the sea to be taken up by sea plants and animals. In places where the bones and excrements of land animals or the sh.e.l.ls and droppings of sea animals acc.u.mulate, deposits of phosphatic material may be built up.
In certain places where great numbers of sea birds congregate, as on desert coasts and oceanic islands, guano deposits have been formed. Some of them, like the worked-out deposits of Peru and Chile, are in arid climates and have been well preserved. Others, like those of the West Indies and Oceania, are subjected to the action of occasional rains; and to a large extent the phosphates have been leached out, carried down, and reprecipitated, permeating and partially replacing the underlying limestones. In this way deposits have been formed containing as high as 85 per cent calcium phosphate.
Even more important bodies of phosphates have been produced by the acc.u.mulation of marine animal remains, probably with the aid of joint chemical, bacterial, and mechanical precipitation. These processes have formed the chief productive deposits of the world, including those of the United States, northern Africa, and Russia, and also the phosphatic iron ores of England and central Europe. The sedimentary features of many phosphate rocks, particularly their oolitic textures, show a marked similarity to the features of the Clinton type of iron ores (pp.
166-167).
The marine phosphate beds originally consist princ.i.p.ally of calcium phosphate and calcium carbonate in varying proportions. Depending on the amount of secondary enrichment, they form two main types of deposits.
The extensive beds of the western United States (in the upper Carboniferous) are hard, and very little enrichment by weathering has taken place; they carry in their richer portions 70 to 80 per cent calcium phosphate, and large sections range only from about 30 to 50 per cent. In the southeastern deposits (Silurian and Devonian in Tennessee and Tertiary in the Carolinas and Florida), there has been considerable enrichment, the rock is softer, and the general grade ranges from 65 to 80 per cent. Both calcium carbonate and calcium phosphate are soluble in ordinary ground waters, but the carbonate is the more soluble of the two. Thus the carbonate has been dissolved out more rapidly, and in addition descending waters carrying the phosphate have frequently deposited it to pick up the carbonate. These enriching processes, sometimes aided by mechanical concentration, have formed high-grade deposits both in the originally phosphatic beds and in various underlying strata. Concretionary and nodular textures are common. The "pebble" deposits of Florida consist of the phosphatic materials broken up and worked over by river waters and advancing shallow seas.
PYRITE
ECONOMIC FEATURES
The princ.i.p.al use of pyrite is in the manufacture of sulphuric acid.
Large quant.i.ties of acid are used in the manufacture of fertilizers from phosphate rock, and during war times in the manufacture of munitions.
Sulphuric acid converts the phosphate rock into superphosphate, which is soluble and available for plant use. Other uses of the acid are referred to in connection with sulphur. Pyrite is also used in Europe for the manufacture of paper from wood-pulp, but in the United States native sulphur has thus far been exclusively used for this purpose. The residue from the roasting of pyrite is a high-grade iron ore material frequently very low in phosphorus, which is desirable in making up mixtures for iron blast furnaces.
Most of the countries of Europe are producers of pyrite, and important amounts are also produced in the United States and Canada. The European production is marketed mainly on that continent, but considerable amounts come to the United States from Spain.
Before the war domestic sources supplied a fourth to a third of the domestic demand for pyrite. Imports came mainly from Spain and Portugal to consuming centers on the Atlantic seaboard. The curtailment of overseas imports of pyrite during the war increased domestic production by about a third and resulted also in drawing more heavily on Canadian supplies, but the total was not sufficient to meet the demand. The demand was met by the increased use of sulphur from domestic deposits (p. 109). At the close of the war supplies of pyrite had been acc.u.mulated to such an extent that, with the prospect of reopening of Spanish importation, pyrite production in the United States practically ceased. War experience has demonstrated the possibility of subst.i.tution of sulphur, which the United States has in large and cheaply mined quant.i.ties. The future of the pyrite industry in the United States therefore looks cloudy, except for supplies used locally, as in the territory tributary to the Great Lakes, and except for small amounts locally recovered as by-products in the mining of coal or from ores of zinc, lead, and copper. Pyrite production in the past has been chiefly in the Appalachian region, particularly in Virginia and New York, and in California.
GEOLOGIC FEATURES
Pyrite, the yellow iron sulphide, is the commonest and most abundant of the metallic sulphides. It is formed under a large variety of conditions and a.s.sociations. Marcasite and pyrrhot.i.te, other iron sulphide minerals, are frequently found with pyrite and are used for the same purposes.
The great deposits of Rio Tinto, Spain, which produce about half of the world's pyrite, were formed by replacement of slates by heated solutions from nearby igneous rocks. The ores are in lenticular bodies, and consist of almost ma.s.sive pyrite with a small amount of quartz and scattered grains and threads of chalcopyrite (copper-iron sulphide).
They carry about 50 per cent of sulphur, and the larger part carries about 2 per cent of copper which is also recovered.
Similar occurrences of pyrite on a smaller scale are known in many places. Pyrite is very commonly found in vein and replacement deposits of gold, silver, copper, lead, and zinc. In the Mississippi valley it is extracted as a by-product from the lead and zinc ores, and in the Cordilleran region large quant.i.ties of by-product pyrite could easily be produced if there were a local demand. The pyrite deposits of the Appalachian region are chiefly lenses in schists; they are of uncertain origin though some are believed to have been formed by replacement of metamorphosed limestones and schists.
Under weathering conditions pyrite oxidizes, the sulphur forming sulphuric acid,--an important agent in the secondary enrichment of copper and other sulphides,--and the iron forming the minerals hemat.i.te and limonite in the shape of a "gossan" or "iron-cap."
Pyrite is likewise frequently found in sediments, apparently being formed mainly by the reducing action of organic matter on iron salts in solution. In Illinois and adjacent states it is obtained as a by-product of coal mining.
SULPHUR
ECONOMIC FEATURES
Sulphur is used for many of the same purposes as pyrite. Under pre-war conditions, the largest use in the United States was in the manufacture of paper pulp by the sulphite process. Minor uses were in agriculture as a fungicide and insecticide, in vulcanizing rubber, and in the manufacture of gunpowder. About 5 per cent of the sulphur of the United States was used in the manufacture of sulphuric acid. During the war this use was greatly increased because of the shortage of pyrite and the large quant.i.ties of sulphuric acid necessary for the manufacture of explosives. The replacement of pyrite by sulphur in the manufacture of sulphuric acid has continued since the war, and in the future is likely to continue to play an important part. Sulphuric acid is an essential material for a great range of manufacturing processes. Some of its more important applications are: in the manufacture of superphosphate fertilizer from phosphate rock; in the refining of petroleum products; in the iron, steel, and c.o.ke industries; in the manufacture of nitroglycerin and other explosives; and in general metallurgical and chemical practice.
The United States is the world's largest sulphur producer. The princ.i.p.al foreign countries producing important amounts of sulphur are Italy, j.a.pan, Spain, and Chile. Europe is the chief market for the Italian sulphur. In spite of increased demands in Europe the Italian production has decreased as the result of unfavorable labor, mining, and transportation conditions, and the deficit has had to be met from the United States. j.a.pan's sulphur production has been increasing. Normally about half of the material exported comes to the United States to supply the needs of the paper industry in the Pacific states, and half goes to Australia and other British colonies. Spain's production is relatively small and has been increasing slowly; most of it is consumed locally.
Chile's small production is mainly consumed at home and large additional amounts are imported.