Читать книгу Elements of Agricultural Chemistry - Thomas Anderson - Страница 8

		Grs.
Rain.	{Paris	0·0708
	{Liebfrauenberg	0·0140
Dew.	{Maximum	0·0785
	{Minimum	0·0030
Fog.	{Paris	0·7092
	{Liebfrauenberg	0·0718

Although it thus appears that Barral's results have been only partially confirmed, enough has been ascertained to show that the quantity of ammonia and nitric acid in the air is sufficient to produce a material influence in the growth of plants. The large amount of these substances contained in the dew is also particularly worthy of notice, and may serve to some extent to explain its remarkably invigorating effect on vegetation.

Carburetted Hydrogen.—Gay-Lussac, Humboldt, and Boussingault have shown, that when the whole of the moisture and carbonic acid have been removed from the air, it still contains a small quantity of carbon and hydrogen; and Saussure has rendered it probable that they exist in a state of combination as carburetted hydrogen gas. No definite proof of this position has, however, as yet been adduced, and the function of the compound is entirely unknown. It is possible that the presence of carbon and hydrogen may be due to a small quantity of organic matter; but, whatever be its source, its amount is certainly extremely small.

Sulphuretted Hydrogen and Phosphuretted Hydrogen.—The proportion of these substances is almost infinitesimal; but they are pretty general constituents of the atmosphere, and are apparently derived from the decomposition of animal and vegetable matters.

The preceding statements lead to the important conclusion, that the atmosphere is capable of affording an abundant supply of all the organic elements of plants, because it not only contains nitrogen and oxygen in the free state, but also in those forms of combination in which they are most readily absorbed, as well as a large quantity of carbonic acid, from which their carbon may be derived. At first sight it may indeed appear that the quantity of the latter compound, and still more that of ammonia, is so trifling as to be of little practical importance. But a very simple calculation serves to show that, though relatively small, they are absolutely large, for the carbonic acid contained in the whole atmosphere amounts in round numbers to

2,400,000,000,000 tons,

and the ammonia, assuming it not to exceed one part in fifty millions, must weigh

74,000,000 tons,

quantities amply sufficient to afford an abundant supply of these elements to the whole vegetation of our globe.

The Soil as a Source of the Organic Constituents of Plants.—When a portion of soil is subjected to heat, it is found that it, like the plant, consists of a combustible and an incombustible part; but while in the plant the incombustible part or ash is small, and the combustible large, these proportions are reversed in the soil, which consists chiefly of inorganic or mineral matters, mixed with a quantity of combustible or organic substances, rarely exceeding 8 or 10 per cent, and often falling considerably short of this quantity.

The organic matter exists in the form of a substance called humus, which must be considered here as a source of the organic constituents of plants, independently of the general composition of the soil, which will be afterwards discussed.

The term humus is generic, and applied by chemists to a rather numerous group of substances, very closely allied in their properties, several of which are generally present in all fertile soils. They have been submitted to examination by various chemists, but by none more accurately than by Mulder and Herman, to whom, indeed, we owe almost all the precise information we possess on the subject. The organic matters of the soil may be divided into three great classes; the first containing those substances which are soluble in water; the second, those extracted by means of caustic potash; and the third, those insoluble in all menstrua. When a soil is boiled with a solution of caustic potash, a deep brown fluid is obtained, from which acids precipitate a dark brown flocculent substance, consisting of a mixture of at least three different acids, to which the names of humic, ulmic, and geic acids have been applied. The fluid from which they have been precipitated contains two substances, crenic and apocrenic acids, while the soil still retains what has been called insoluble humus.

The acids above named do not differ greatly in chemical characters, but they have been subdivided into the humic, geic, and crenic groups, which present some differences in properties and composition. They are compounds of carbon, hydrogen, and oxygen, and are characterised by so powerful an affinity for ammonia that they are with difficulty obtained free from that substance, and generally exist in the soil in combination with it. They are all products of the decomposition of vegetable matters in the soil, and are formed during their decay by a succession of changes, which may be easily traced by observing the course of events when a piece of wood or any other vegetable substance is exposed for a length of time to air and moisture. It is then found gradually to disintegrate with the evolution of carbonic acid, acquiring first a brown and finally a black colour. At one particular stage of the process it is converted into one or other of two substances, called humin and ulmin, both insoluble in alkalies, and apparently identical with the insoluble humus of the soil; but when the decomposition is more advanced the products become soluble in alkalies, and then contain humic, ulmic, and geic acids, and finally, by a still further progress, crenic and apocrenic acids are formed as the result of an oxidation occurring at certain periods of the decay.

The roots and other vegetable debris remaining in the soil undergo a similar series of changes, and form the humus, which is found only in the surface soil, that is to say, in the portion which is now or has at some previous period been occupied by plants, and the quantity of humus contained in any soil is mainly dependent on the activity of vegetation on it. Numerous analyses of humus compounds extracted from the soil have been made, and have served to establish a number of minor differences in the composition even of those to which the same name has been applied, due manifestly to the fact that their production is the result of a gradual decomposition, which renders it impossible to extract from the soil one pure substance, but only a variable mixture of several, so similar to one another in properties, that their separation is very difficult, if not impossible. For this reason great discrepancies exist in the statements made regarding them by different observers, but this is a matter of comparatively small importance, as their exact composition has no very direct bearing on agricultural questions, and it will suffice to give the names and chemical formulæ of those which have been analysed and described—

Ulmic acid from long Frisian turf	C40	H18	O16
Humic acid from hard turf	C40	H15	O15
Humic acid from arable soil	C40	H16	O16
Humic acid from a pasture field	C40	H14	O14
Geic acid	C40	H15	O17
Apocrenic acid	C48	H12	O24
Crenic acid	C24	H12	O16

It is only necessary to observe further, that these formulæ indicate a close connection with woody fibre, and the continuous diminution of the hydrogen and increase of oxygen shows that they must have been produced by a gradually advancing decay.

The earlier chemists and vegetable physiologists attributed to the humus of the soil a much more important function than it is now believed to possess.

It was formerly considered to be the exclusive, or at least the chief source of the organic constituents of plants, and by absorption through the roots to yield to them the greater part of their nutriment. But though this view has still some supporters, among whom Mulder is the most distinguished, it is now generally admitted that humus is not a direct source of the organic constituents of plants, and is not absorbed as such by their roots, although it is so indirectly, in as far as the decomposition which it is constantly undergoing in the soil yields carbonic acid, which can be absorbed. The older opinion is refuted by many well-ascertained facts. As regards the exclusive origin of the carbon of plants from humus, it is easy to see that this at least cannot be true, for humus, as already stated, is itself derived solely from the decomposition of vegetable and animal matters; and if the plants on the earth's surface were to be supported by it alone, the whole of their substance would have to return to the soil in the same form, in order to supply the generation which succeeds them. But this is very far from being the case, for the respiration of animals, the combustion of fuel, and many other processes, are annually converting a large quantity of these matters into carbonic acid; and if there were no other source of carbon but the humus of the soil, the amount of vegetable life would gradually diminish, and at length become entirely extinct. Schleiden, who has discussed this subject very fully, has made an approximative calculation of the total quantity of humus on the earth's surface, and of the carbon annually converted into carbonic acid by the respiration of man and animals, the combustion of wood for fuel, and other minor processes; and he draws the conclusion that, if there were no other source of carbon except humus, the quantity of that substance existing in the soil would only support vegetation for a period of sixty years.

The particular phenomena of vegetation also afford abundant evidence that humus cannot be the only source of carbon. Thus Boussingault has shown that on the average of years, the crops cultivated on an acre of land remove from it about one ton more organic matter than they receive in the manure applied to them, although there is no corresponding diminution in the quantity of humus contained in the soil. An instance which leads still more unequivocally to the same conclusion is given by Humboldt. He states that an acre of land, planted with bananas, yields annually about 152,000 pounds weight of fruit, containing about 32,000 pounds, or almost exactly 14 tons of carbon; and as this production goes on during a period of twenty years, there must be withdrawn in that time no less than 280 tons of carbon. But the soil on an acre of land weighs, in round numbers, 1000 tons, and supposing it to contain 4 per cent of humus, the total weight of carbon in it would amount to little more than 20 tons.

It is obvious from these and many other analogous facts that humus cannot be the only or even a considerable source of the carbon of plants, although it is still contended by some chemists that it may be absorbed to a small extent. But even this is at variance with many well-known facts. For if humus were absorbed, it might be expected that vegetation would be most luxuriant on soils containing abundance of that substance, especially if it existed in a soluble and readily absorbable form; but so far from this being the case, nothing is more certain than that peat, in which these conditions are fulfilled, is positively injurious to most plants. On the other hand, our daily experience affords innumerable examples of plants growing luxuriantly in soils and places where no humus exists. The sands of the sea-shore, and the most barren rocks, have their vegetation, and the red-hot ashes which are thrown out by active volcanoes are no sooner cool than a crop of plants springs up on them.

The conclusions to be drawn from these considerations have been further confirmed by the direct experiments of different observers. Boussingault sowed peas, weighing 15·60 grains, in a soil composed of a mixture of sand and clay, which had been heated red-hot, and consequently contained no humus, and after 99 days' growth, during which they had been watered with distilled water, he found the crop to weigh 68·72 grains, so that there had been a fourfold increase. Similar experiments have been made by Prince Salm Horstmar, on oats and rape sown in a soil deprived of organic matter by ignition, in which they grew readily, and arrived at complete maturity. One oat straw attained a height of three feet, and bore 78 grains; another bore 47; and a third 28—in all 153. These when dried at 212° weighed 46·302 grains, and the straw 45·6 grains. The most satisfactory experiments, however, are those of Weigman and Polstorf, these observers having found that it was possible to obtain a two-hundred-fold produce of barley in an entirely artificial soil, provided care was taken to give it the physical characters of a fertile soil. They prepared a mixture of six parts of sand, two of chalk, one of white bole, and one of wood charcoal; to which was added a small quantity of felspar, previously fused with marble and some soluble salts, so as to imitate as closely as possible the inorganic parts of a soil, and in it they planted twelve barley pickles. The plants grew luxuriantly, reaching a height of three feet, and each bearing nine ears, containing 22 pickles. The grain of the twelve plants weighed 2040 grains.

These experiments show that plants can grow and produce seed when the most scrupulous care is taken to deprive them of every trace of humus. But Saussure has gone further, and shown that even when present, humus is not absorbed. He allowed plants of the common bean and the Polygonum Persicaria to grow in solutions of humate of potash, and found a very trifling diminution in the quantity of humic acid present; but the value of his experiments is invalidated by his having omitted to ascertain whether the diminution of humic acid which he observed was really due to absorption by the plant. This omission has been supplied by Weigman and Polstorf. They grew plants of mint (Mentha undulata) and of Polygonum Persicaria in solutions of humate of potash, and placed beside the glass containing the plant, another perfectly similar, and containing only the solution of humate of potash. The solution, which contained in every 100 grains, 0·148 grains of solid matter, consisting of humate of potash, etc. was found to become gradually paler, and at the end of a month, during which time the plants had increased by 6–½ inches, the quantity of solid matter in 100 grains had diminished to 0·132. But the solution contained in the other glass, and in which no plant had grown, had diminished to 0·136, so that the absorption could not have amounted to more than 0·004 grains for every 100 grains of solution employed. This quantity is so small as to be within the limits of error of experiment, and we are consequently entitled to draw the conclusion that humus, even under the most favourable circumstances, is not absorbed by plants.

But though not directly capable of affording nutriment to plants, it must not, on that account, be supposed that humus is altogether devoid of importance, for it is constantly undergoing decomposition in the soil, and thus becomes a source of carbonic acid which can be absorbed, and, as we shall afterwards more particularly see, it exercises very important functions in bringing the other constituents of the soil into readily available forms of combination.

It has been already observed that carbon, hydrogen, nitrogen, and oxygen, cannot be absorbed by plants when uncombined, but only in the forms of water, carbonic acid, ammonia, and nitric acid. It is scarcely necessary to detail the grounds on which this conclusion has been arrived at in regard to carbon and hydrogen, for practically it is of little importance whether they can be absorbed or not, as the former is rarely, the latter never, found uncombined in nature. Neither can there be any doubt that water and carbonic acid are the only substances from which these elements can be obtained. Every-day experience convinces us that water is essential to vegetation; and Saussure, and other observers, have shown that plants will not grow if they are deprived of carbonic acid, and that they actually absorb that substance abundantly from the atmosphere. The evidence for the non-absorption of oxygen lies chiefly in the fact that plants obtain, in the form of water and carbonic acid, a larger quantity of that element than they require, and in place of absorbing, are constantly exhaling it. The form in which nitrogen may be absorbed has given rise to much difference of opinion. In the year 1779, Priestley commenced the examination of this subject, and drew from his experiments the conclusion, that plants absorb the nitrogen of the air. Saussure shortly afterwards examined the same subject, and having found, that when grown in a confined space of air, and watered with pure water, the nitrogen of the plants underwent no increase, he inferred that they derived their entire supplies of that element from ammonia, or the soluble nitrogenous constituents of the soil or manure. Boussingault has since re-examined this question, and by a most elaborate series of experiments, in which the utmost care was taken to avoid every source of fallacy, he was led to the conclusion, that when haricots, oats, lupins, and cresses were grown in calcined pumice-stone, mixed with the ash of plants, and supplied with air deprived of ammonia and nitric acid, their nitrogen underwent no increase. It has been objected to these experiments, that the plants being confined in a limited bulk of air, were placed in an unnatural condition, and Ville has recently repeated them with a current of air passing through the apparatus, and found a slight increase in the nitrogen, due, as he thinks, to direct absorption. It is much more probable, however, that it depends on small quantities of ammonia or nitric acid which had not been completely removed from the air by the means employed for that purpose, for nothing is more difficult than the complete abstraction of these substances, and as the gain of nitrogen was only 0·8 grains, while 60,000 gallons of air, and 13 of water, were employed in the experiment, which lasted for a considerable time, it is reasonable to suppose that a sufficient quantity may have remained to produce this trifling increase.

While these experiments show that plants maintain only a languid existence when grown in air deprived of ammonia and nitric acid, and hence, that the direct absorption of nitrogen, if it occur at all, must do so to a very small extent, the addition of a very minute quantity of the former substance immediately produces an active vegetation and rapid increase in size of the plants. Among the most striking proofs of this are the experiments of Wolff, made by growing barley and vetches in a soil calcined so as to destroy organic matters, and then mixed with small quantities of different compounds of ammonia. He found that when the produce from the calcined soil was represented by 100, that from the different ammoniacal salts was—

	Barley.	Vetches.
Muriate of Ammonia	257·2	176·4
Carbonate of Ammonia	123·6	173·8
Sulphate of Ammonia	203·6	125·2

These experiments not only prove that ammonia can be absorbed, but they also indirectly confirm the statement already made, that humus is not necessary; for in some instances the produce was higher than that obtained from the uncalcined soil with the same manures, although it contained four per cent of humus.

On such experiments Liebig rests his opinion that ammonia is the exclusive source of the nitrogen of plants, and although he has recently admitted that it may be replaced by nitric acid, it is obvious that he considers this a rare and exceptional occurrence. The evidence, however, for the absorption of nitric acid appears to rest on as good grounds as that of ammonia, for experience has shown that nitrate of soda acts powerfully as a manure, and its effect must be due to the nitric acid, and not to the soda, for the other compounds of that alkali have no such effect. Wolff has illustrated this point by a series of experiments on the sunflower, of which we shall quote one. He took two seeds of that plant, and sowed them on the 10th May, in a soil composed of calcined sand, mixed with a small quantity of the ash of plants, and added at intervals during the progress of the experiment, a quantity of nitrate of potash, amounting in all to 17·13 grains. The plants were watered with distilled water, containing carbonic acid in solution, and the pot in which they grew was protected from rain and dew by a glass cover. On the 19th August one of the plants had attained a height of above 28 inches, and had nine fine leaves and a flower-bud; the other was about 20 inches high, and had ten leaves. On the 22d August, one of the plants having been accidentally injured, the experiment was terminated. The plants, which contained 103·16 grains of dry matter, were then carefully analysed, and the quantity of nitrogen contained in the soil after the experiment and in the seed was determined.

		Grains.
Nitrogen	in the dry plants	1·737	}
"	remaining in the soil	0·697	}	2·434
"	in the nitrate of potash	2·370	}
"	in the seeds	0·029	}	2·399
				———
	Difference		0·035

Hence, the nitrogen contained in the plants must, in this instance, have been obtained entirely from the nitrate of potash, for the quantity contained in it and in the seeds is exactly equal to that in the plants and the soil, the difference of 0·03 grains being so small that it may be safely attributed to the errors inseparable from such experiments. For the sake of comparison, an exactly similar experiment was made on two seeds grown without nitrate of potash, and in this instance, after an equally long period of growth, the largest plant had only attained a height of 7·5 inches, and had three small pale and imperfectly developed leaves. They contained only 0·033 grains of nitrogen, while the seeds contained 0·032—indicating that, under these circumstances, there was no increase in the quantity of that element.

But, independently of these experimental results, it may be inferred from general considerations, that nitric acid must be one of the sources from which plants derive their nitrogen. It has been already stated, that the humus contained in the soil consists of the remains of decayed plants, and there is every reason to suppose that the primeval soil contained no organic matters, and that the first generation of plants must have derived the whole of their nitrogen from, the atmosphere. If, therefore, it be assumed that ammonia is the only source of the nitrogen of plants, it would follow, that as that substance cannot be produced by the direct union of its elements, the quantity of ammonia in the air could only remain undiminished in the event of the whole of the nitrogen of decaying plants returning into that form. But this is certainly not the case, for every time a vegetable substance is burned, part of its nitrogen is liberated in the free state, and in certain conditions of putrefaction, nitric acid is produced. Now, if ammonia be the only form in which nitrogen is absorbed, there must be a gradual diminution of the quantity contained in the air; and further, there must either be some continuous source of supply by which its quantity is maintained, or there must be some other substance capable of affording nitrogen in a form fitted for the maintenance of plant life. As regards the first alternative, it must be stated that we know of no source other than the decomposition of plants from which ammonia can be derived, and we are therefore compelled to adopt the second alternative, and to admit that there must be some other source of nitrogen, and it cannot be doubted, from what has been already stated, that it is from nitric acid only that it can be obtained.

It must be admitted, then, that carbonic acid, ammonia, nitric acid, and water, are the great organic foods of plants. But while they have afforded to them an inexhaustible supply of the last, the quantity of the other three available for food are limited, and insufficient to sustain their life for a prolonged period. It has been shown by Chevandrier, that an acre of land under beech wood accumulates annually about 1650 lb. of carbon. Now, the column of air resting upon an acre of land contains only about 15,500 lb. of carbon, and the soil may be estimated to contain 1 per cent., or 22,400 lb. per acre, and the whole of this carbon would therefore be removed, both from the air and the soil, in the course of little more than 23 years. But it is a familiar fact, that plants continue to grow with undiminished luxuriance year after year in the same soil, and they do so because neither their carbon nor their nitrogen are permanently absorbed; they are there only for a period, and when the plant has finished its functions, and dies, they sooner or later return into their original state. Either the plant decays, in which case its carbon and nitrogen pass more or less rapidly into their original state, or it becomes the food of animals, and by the processes of respiration and secretion, the same change is indirectly effected. In this way a sort of balance is sustained; the carbon, which at one moment is absorbed by the plant, passes in the next into the tissues of the animal, only to be again expired in that state in which it is fitted to commence again its round of changes.

But while there is thus a continuous circulation of these constituents through both plants and animals, there are various changes which tend to liberate in the free state a certain quantity both of the carbon and nitrogen of plants, and these being thus removed from the sphere of organic life, there would be a gradual diminution in the amount of vegetation at the earth's surface, unless this loss were counterbalanced by some corresponding source of gain. In regard to carbonic acid the most important source is volcanic action, but the loss of nitrogen, which is far more important and considerable, is restored by the direct combination of its elements. The formation of nitric acid during thunder storms has been long familiar; but it would appear from the recent experiments of Clöez, which, should they be confirmed by farther enquiry, will be of much importance, that this compound is also produced without electrical action when air is passed over certain porous substances, saturated with alkaline and earthy compounds. Fragments of calcined brick and pumice stone were saturated with solution of carbonate of potash, with carbonates of lime and magnesia and other mixtures, and a current of air freed from nitric acid and ammonia passed over them for a long period, at the end of which notable quantities of nitric acid were detected.

Source of the Inorganic Constituents of Plants.—The inorganic constituents of plants being all fixed substances, it is sufficiently obvious that they can only be obtained from the soil, which, as we shall afterwards see, contains all of them in greater or less abundance, and has always been admitted to be the only substance capable of supplying them. The older chemists and physiologists, however, attributed no importance to these substances, and from the small quantities in which they are found in plants, imagined that they were there merely accidental impurities absorbed from the soil along with the humus, which was at that time considered to be their organic food. This opinion, sufficiently disproved by the constant occurrence of the same substances in nearly the same proportions, in the ash of each individual plant, has been further refuted by the experiments of Prince Salm Horstmar, who has established their importance to vegetation, by experiments upon oats grown on artificial soils, in each of which one inorganic constituent was omitted. He found that, without silica, the grain vegetated, but remained small, pale in colour, and so weak as to be incapable of supporting itself; without lime, it died when it had produced its second leaf; without potash and soda, it grew only to the height of three inches; without magnesia, it was weak and incapable of supporting itself; without phosphoric acid, weak but upright; and without sulphuric acid, though normal in form, the plant was feeble, and produced no fruit.

Manner in which the Constituents of Plants are absorbed.—Having treated of the sources of the elements of plants, it is necessary to direct attention to the mode in which they enter their system.

Water.—The absorption of water by plants takes place in great abundance, and is connected with many of the most important phenomena of vegetation. It is principally absorbed by the roots, and passes into the tissues of the plant, where a part of it is decomposed, and goes to the formation of certain of its organic compounds; while by far the larger quantity, in place of remaining in it, is again exhaled by the leaves. The extent to which this takes place is very large. Hales found that a sunflower exhaled in twelve hours about 1 lb. 5 oz. of water, but this quantity was liable to considerable variation, being greater in dry, and less in wet weather, and much diminished during the night. Saussure made similar experiments, and observed that the quantity of water exhaled by a sunflower amounted to about 220 lb. in four months. The exhalation of plants has recently been examined with great accuracy by Lawes. His experiments were made by planting single plants of wheat, barley, beans, peas, and clover, in large glass jars capable of holding about 42 lb. of soil, and covered with glass plates, furnished with a hole in the centre for the passage of the stem of the plant. Water was supplied to the soil at certain intervals, and the jars were carefully weighed. The result of the experiments, continued during a period of 172 days, is given in the following table, which shows the total quantity of water exhaled in grains:—

Wheat	113,527
Barley	120,025
Beans	112,231
Peas	109,082
Clover, cut 28th June	55,093

It further appears, that the exhalation is not uniform, but increases during the active growth of the plant, and diminishes again when that period is passed. These variations are shown by the subjoined tables, of which the first gives the total exhalation, and the second the average daily loss of water during certain periods.