CHAPTER IV. NITRIFICATION.

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The most important compound of nitrogen for the plant is nitric acid. It is as nitrates that most plants absorb the nitrogen they require to build up their tissue. In nature the nitrogen, present in the soil as ammonia and different organic forms, is constantly being converted into nitric acid. This conversion of nitrogen into nitrates, known as nitrification, is a process of very great importance, and, as has been already pointed out in the Introductory Chapter, is effected through the agency of micro-organisms (ferments).[97] The process of nitrification, as well as the nature of the other changes taking place in the soil between the various compounds of nitrogen, are as yet but most imperfectly understood, but much light has been thrown on this most interesting department of agricultural research during the last few years; and it cannot be doubted that the increased attention which it is receiving from different investigators, both on the Continent and in this country, will be fraught with most important results for practical agriculture.

Occurrence of Nitrates in the Soil.

The occurrence of nitre,[98] or potassium nitrate, in soils has been long known, although it is only within the last few years that we have obtained any precise knowledge with regard to the mode of its production. While its amount in most soils, especially in this country,[99] is very minute, there are certain parts of the world where nitrates are found in large quantities. The nitrate fields of Chili and Peru are the chief natural sources of nitrates, and they are referred to in the chapter on Nitrate of Soda. We have other parts of the world, however (in China and India), where soils rich in nitre occur, and which in the past have formed a source of the commercial article.[100]

Nitre Soils of India.

The most important of these nitre soils are those found in the North-west of India, in the province of Bengal. In these districts the soil is of a light porous texture, rich in lime, and situated at a considerable height above water-level. They are the sites of old villages, and the nitre is found in the form of an efflorescence on the surface of different parts of the soil. The occurrence of nitre under such conditions is due, partly to the natural richness of the soil in nitrogen, and partly to its artificial enrichment through receiving the nitrogenous excrements of the inhabitants of the villages and their cattle. The constant process of evaporation going on in such a warm climate has the effect of inducing an upward tendency of the soil-water, the result being a concentration of all the nitre the soil contains in its surface layer. This goes on until a regular incrustation is formed, and the soil is covered by a white deposit of nitre. Whenever this becomes apparent, the surface portion of the soil is scraped off by the sorawallah, or native manufacturer, and collected and treated for the purpose of recovering, in a pure state, the saltpetre.

Saltpetre Plantations.

The large demand for saltpetre, larger than could be supplied by these nitre soils, soon gave rise to the semi-artificial method of production, formerly so largely practised in Switzerland, France, Germany, Sweden, and in many other parts of the Continent, by means of the so-called "nitre beds," "nitraries," or "saltpetre plantations." Previous to the introduction of this method of manufacture, the demand for saltpetre for gunpowder had become so great, that every source of nitre was eagerly sought for. Thus, when it was discovered that the earth from the floors of byres, stables, and farmyards were particularly rich in nitre, and when mixed with wood-ashes formed an important source of it, the right to remove these in France was vested in the Government under the Saltpetre Laws, which obtained till the French Revolution. This great scarcity soon led, however, to a careful investigation being made into the conditions under which potassium nitrate was formed in nitre soils.[101] These conditions, which included the presence of rich nitrogenous matter, warmth, free aeration of the soil, and a certain proportion of moisture, became, in the course of years, more and more thoroughly understood, and the result was the institution of numerous "saltpetre plantations." These generally consisted of heaps of mould, rich in nitrogen, mixed with decomposing animal matter, rubbish of various kinds, manurial substances, ashes, road-scrapings, and lime salts.[102] The heap was interlaid with brushwood, and was watered from time to time with liquid manure from stables, consisting chiefly of dilute urine. In forming the heap care was taken to keep the mass porous, so as to admit of the free access of air. The heap was further protected from the rain by covering it with a roof. In course of time considerable quantities of nitrates were developed, and the nitre was occasionally collected by scraping it from the surface, where it became concentrated just as in the nitre soils. In all cases, however, the heaps, when considered rich enough in nitre, were treated from time to time with water which, by subsequent evaporation, yielded the nitre in a more or less pure condition.[103]

This mode of obtaining nitre is no longer practised to any extent, since it is now more conveniently obtained from the treatment of nitrate of soda with potassium chloride.

Cause of Nitrification.

We have adverted to these nitre plantations as showing how the conditions most favourable for the development of nitrification were recognised long before anything was known as to the true nature of the process. It was only in 1877 that the formation of nitrates in the soil was proved to be due to the action of micro-organic life,[104] by the two French chemists, Schloesing and MÜntz, who discovered the fact when carrying out experiments to see if the presence of humic matter was essential to the purification of sewage by soil. In these experiments sewage was made to filter slowly through a certain depth of soil (the time occupied in this filtration being eight days). It was found that nitrification of the sewage took place. By treating the soil with chloroform[105] it was found that it no longer possessed the power of inducing the nitrification of the sewage. When, however, a small portion of a nitrifying soil was added, the power was regained. From this it was naturally inferred that nitrification was effected by some kind of ferment. This conclusion was soon confirmed by subsequent experiments by Warington at Rothamsted, who showed that the power of nitrification could be communicated to media, which did not nitrify, by simply seeding them with a nitrifying substance, and that light was unfavourable to the process. Since then the question has formed the subject of a number of researches by Mr Warington at Rothamsted, as well as by Schloesing and MÜntz, Munro, DehÉrain, P. F. Frankland, Winogradsky, Gayon and Dupetit, Kellner, Plath, Pichard, Landolt, Leone, and others. From these researches we have obtained the following information with regard to the nature of the organisms concerned in this process, and the conditions most favourable for their development.

Ferments effecting Nitrification.

The importance of isolating and studying them microscopically was recognised at an early period in these researches. Messrs Schloesing and MÜntz were the first to attempt this. They reported that they had successfully accomplished this, and described the organism as consisting of very small, round, or slightly elongated corpuscles, occurring either singly or two together. According, however, to the most recent researches of Warington, Winogradsky, and P. F. Frankland, nitrification is not effected by a single micro-organism, but by two, both of which have been successfully isolated and studied.[106] The first of these to be discovered and isolated was the nitrous organism, which effects the conversion of ammonia into nitrous acid; the second, which has only been lately isolated by Warington and Winogradsky, effects the conversion of nitrous acid into nitric acid. Each of these ferments thus has its distinctive function to perform in this most important process, the nitric ferment being unable to act on ammonia, as the nitrous ferment is unable to convert nitrites into nitrates. Both ferments occur in enormous quantities in the soil, and seem to be influenced, so far as is at present known, by the same conditions. Their action will thus proceed together. Nearly all we know as yet on the subject of their nature is with regard to the nitrous ferment.

Appearance of Nitrous Organism.

Mr Warington[107] thus describes the appearance of the nitrous organism: "As found in suspension in a freshly nitrified solution, it consists largely of nearly spherical corpuscles, varying extremely in size. The largest of these corpuscles barely reaches a diameter of 1/1000th of a millimeter; and some are so minute as to be hardly discernible in photographs, although shown there with a surface one million times greater than their own. The larger ones are frequently not strictly circular. These forms are universally present in nitrifying cultures. The larger organisms are sometimes seen in the act of dividing."

Nitric Organism.

So far as at present known, the nitric organism is very similar in appearance to the nitrous organism, so much so that it is difficult to distinguish the one from the other. As the same conditions influence their development, the process may be regarded as a whole.

Difficulty in isolating them.

A great difficulty has been experienced in the attempt to isolate these micro-organisms for the purpose of studying their nature. This arises from the fact that they refuse to grow on the ordinary solid cultivating media used by bacteriologists. Winogradsky, however, has recently succeeded in cultivating them in a purely mineral medium—viz., silica-jelly.[108]

Nitrifying Organisms do not require Organic Matter.

The fact that they can develop in media destitute of organic matter, is one of very great interest and importance to Vegetable Physiology. It implies that they can derive their carbon from carbonic acid—a power which it was believed was possessed by green plants alone among living structures. For organisms destitute of chlorophyll, the source of their protoplasmic carbon, it has been hitherto commonly believed, must be organic matter of some sort. While it would appear that the nitrifying organisms can, when opportunity affords, feed upon organic matter, yet it has been proved beyond doubt that they can also freely develop in media entirely devoid of it, and are capable, under such circumstances, of deriving their carbon from a purely mineral source.[109] This fact, which is subversive of what was believed to be a fundamental law of Vegetable Physiology, is one of the most important of the many important and interesting facts which these nitrification researches have elicited.[110]

Conditions favourable for Nitrification.

We may now proceed to discuss the conditions favourable for nitrification.

Presence of Food-constituents.

Among these conditions the first is the presence of certain food-constituents. To both animal and vegetable life alike a certain amount of mineral food is absolutely necessary. Among these phosphoric acid is one of the most important, and in the experiments on nitrification it has been found that the nitrifying organisms will not develop in any medium destitute of it. That other mineral food-constituents are necessary is highly probable, although the influence of their absence on the development of the process has not been similarly studied. Probably potash, magnesia, and lime salts are necessary. In the cultivating solutions used in the experiments on the subject, the mineral food-constituents added consisted of lime, magnesia, and potash salts and phosphoric acid.[111]

As we have seen above, the presence of organic matter is not necessary for the process. In this respect these organisms are differentiated from all other ferments hitherto discovered.

Presence of a Salifiable Base.

The presence of a sufficient quantity of a base in the soil with which the nitric acid may combine, when it is formed, is another necessary condition.[112] The process only goes on in a slightly alkaline solution. The substance which acts as this salifiable base is lime. The presence of a sufficient quantity of carbonate of lime in the soil will thus be seen to be of first-rate importance. This furnishes an explanation of one of the many benefits conferred by lime on soils. The activity of nitrification in many soils may be hindered by the absence of a sufficiency of lime salts, and in such cases most striking results may follow the application of moderate dressings of chalk. The absence of the nitrifying organisms in certain soils, such as peaty and forest soils, may be thus accounted for. In such soils humic acids are present and the requisite alkalinity is thus awanting.

Only takes place in slightly Alkaline Solutions.

But while a certain slight amount of alkalinity is necessary, this must not exceed a certain strength, otherwise the process is retarded. This is the reason why strong urine solutions do not nitrify. The amount of carbonate of ammonia generated in them by putrefaction renders the development of nitrification impossible by rendering the alkalinity of the solution too great.[113] The practical importance of this fact is considerable, as it shows the importance of diluting urine very considerably before applying it as a manure. Similarly, when large quantities of lime, especially burnt lime, are applied to soils, the result will be to arrest the action of nitrification for the time. The presence of alkaline carbonates in the soil, unless in minute quantities, is apt, therefore, to seriously interfere with the process.[114]

Action of Gypsum on Nitrification.

It has been found by Pichard that the action of certain mineral sulphates is extremely favourable to the process, and among these gypsum. Warington has carried out some experiments on the action of gypsum in promoting nitrification. The reason of its favourable action is probably because it neutralises the alkalinity of nitrifying solutions. It thus permits the process to go on in unfavourable conditions. Where, therefore, too great alkalinity exists for the maximum development of nitrification, the best specific will be found to be gypsum.[115] The practical value of gypsum as an adjunct to certain manurial substances, where nitrification is desired to be promoted as rapidly as possible, such as sewage and farmyard manure, will thus at once become apparent. So far as there is a proper degree of alkalinity maintained, the presence of large quantities of saline matter does not seem to interfere with the process.

Presence of Oxygen.

The nitrification bacteria belong, it would seem, to the aerobic[116] class of ferment—i.e., they cannot develop without a free supply of oxygen. Exclusion of the air is sufficient to kill them, and in those portions of the soil where access of air is not freely permitted, nitrification will be found to be correspondingly feeble. Thus it has been found in experiments with different portions of soils, that but little signs of nitrification occur in the lower soil layers. According to experiments by Schloesing on a moist soil, in atmospheres respectively containing no oxygen and varying quantities of it, the action of oxygen in promoting nitrification was strikingly demonstrated. In an atmosphere of pure nitrogen, entirely devoid of oxygen, the process no longer took place, but the nitrates already present in the soil were reduced and free nitrogen was evolved. In an atmosphere, on the other hand, containing 1.5 per cent of oxygen, a considerable amount of nitrification took place; while in the presence of 6 per cent, nitrification took place to double the extent. An addition of 10 to 15 per cent again doubled the quantity. When the amount of moisture added was increased, the effect of larger percentages of oxygen was found to be less marked. The reason of this is that the oxygen probably acts as dissolved oxygen; the addition of water meaning at the same time an addition of available oxygen. This condition exemplifies the value of tillage operations. The more thoroughly a soil is tilled the more thoroughly will the aeration of its particles take place, and consequently the more favourable will this necessary condition of nitrification be rendered. The benefits conferred on clayey soils by tillage will in this respect be especially great.

Temperature.

Another of the conditions determining the rate at which nitrification takes place, and one which is most important, is Temperature. According to Schloesing and MÜntz the temperature at which maximum development takes place is 37° C.[117] (99° F.), at which temperature it is ten times as active as at 14° C. (57° F.) Below 5° C. (40° F.) the action is extremely feeble. It is clearly appreciable at 12° C. (54° F.), and from there up to 37° C. (99° F.) it rapidly increases. From 37° C. (99° F.) to 55° C. (131° F.), at which temperature no nitrification takes place, its activity decreases; at 45° C. (113° F.) it is less active than at 15° C. (59° F.), and at 50° C. (122° F.) it is very slight. These results by Schloesing and MÜntz have not been exactly confirmed by Warington. He has found that a considerable amount of nitrification goes on at a temperature between 3° and 4° C. (37° and 39° F.), while the highest temperature at which he has found it to take place is considerably lower than 55° C. (131° F.) Thus he was unable to start nitrification in a solution maintained at 40° C. (104° F.) It would thus seem that the nitrifying ferments are able to develop at lower temperatures than most organisms; and although nitrification entirely ceases during frost, yet in a climate such as our own there must be a considerable proportion of the winter during which nitrification is moderately active.

Presence of a sufficient quantity of Moisture.

The presence of moisture in a soil is another of the necessary conditions of nitrification. It has been shown that it is at once arrested, and indeed destroyed, by desiccation. Other conditions being equal, and up to a certain extent, the more moisture a soil contains the more rapid is the process. Too much water, however, is unfavourable, as it is apt to exclude the free access of air, which, as we have just shown, is so necessary, as well as to lower the temperature. During a period of drought the rate at which nitrification takes place will, therefore, be apt to be seriously diminished.

Absence of strong Sunlight.

It has been found that the process goes on much more actively in darkness; indeed Warington has found in his experiments that nitrification could be arrested by simply exposing the vessel in which it was going on to the action of sunshine.

Nitrifying Organisms destroyed by Poisons.

It has already been pointed out that nitrification is arrested by the action of antiseptics, such as chloroform, bisulphide of carbon, and carbolic acid. Another substance which has been found to have an injurious action is ferrous sulphate or "copperas," a substance which is apt to be present in badly drained soils, or soils in which there is much actively putrefying organic matter. Maercker has found that in moor soils containing ferrous sulphate, no nitrates, or mere traces of nitrates, could be found. A substance such as gas-lime, unless submitted to the action of the atmosphere for some time, would also have a bad effect in checking nitrification, owing to the poisonous sulphur compounds it contains. Common salt, it would seem, also arrests the process; and this antiseptic property which salt exercises on nitrification throws a certain amount of light on the nature of its action when applied, as it is often done, along with artificial nitrogenous manures.

Denitrification.

In connection with the process of nitrification, it is of interest to notice that a process of an opposite nature may also take place in soils—viz., denitrification—a process which consists in reducing the nitrates to nitrites, nitrous oxide, or free nitrogen. That a reduction of nitrates takes place in the decomposition of sewage with the evolution of free nitrogen, was a fact first observed by the late Dr Angus Smith in 1867; and the reduction of nitrates to nitrites, and nitric and nitrous oxides in putrefactive changes has been subsequently noticed by different experimenters, who have further observed that such reduction takes place in the case of putrefaction going on in the presence of large quantities of water or where there is much organic matter.

Denitrification also effected by Bacteria.

This change was supposed to be of a purely chemical nature, and it has only been recently discovered that it is effected, like nitrification, by means of bacteria. It has been surmised by some that the action of denitrification may be effected by the same organisms that effect nitrification, and that it depends on merely external conditions which process goes on. There is no reason, however, to suppose that this is so, and several of the denitrifying organisms have been identified.

Conditions favourable for Denitrification.

That it is a process that goes on to any extent in properly cultivated soils is not to be supposed. The conditions which favour denitrification are exactly the opposite of those which favour nitrification. It is only when oxygen is excluded, or, which practically means the same thing, when large quantities of organic matter are in active putrefaction, and the supply of oxygen is therefore deficient, that denitrification takes place. Schloesing, as we have already seen, found that in the case of a moist soil, kept in an atmosphere devoid of oxygen, a reduction of its nitrates to free nitrogen took place.

Takes place in water-logged Soils.

The exclusion of oxygen from a soil may be effected by saturating the soil with water; and Warington has found in experiments carried out in an arable soil, by no means rich in organic matter, that complete reduction of nitrates may be effected in this way. It would thus seem that the process of denitrification will take place in water-logged soils, or in the putrefaction of sewage matter in the presence of large quantities of water. Whether this reduction will result in the production of nitrites, nitrous oxide, or free nitrogen, depends on different conditions. This process is one of great importance from an economic point of view, as it reveals to us a source of loss which may take place in the fermentation of manures. In the rotting of our farmyard manure it is possible that the denitrifying organisms may be more active than we have hitherto suspected, and that a considerable loss of nitrogen may in this way be effected.

Distribution of the Nitrifying Organisms in the Soil.

The nitrifying organisms are probably chiefly confined to the soil, and do not usually occur in rain or in the atmosphere. That, however, they are found in spots which we might be inclined to think extremely unlikely, is shown by some recent interesting researches carried out by MÜntz, who discovered that the bare surfaces of felspathic, calcareous, schistose, and other rocks at the summit of mountains in the Pyrenees, Alps, and Vosges, yielded large numbers of them, and that they occurred to a considerable depth in the cracks and fissures of the rocks. The nitrifying organisms are also found in river-water, in sewage, and well-waters.

Depth down at which they occur.

In Warington's earlier experiments, the conclusion he arrived at was that the occurrence of the nitrifying organisms was almost entirely limited to the superficial layers of the soil, and that they were seldom to be met with much below a depth of 18 inches. His subsequent experiments, however, considerably modified this conclusion, and showed that nitrification may take place to a depth of at least 6 feet.[118] But although it may take place at this depth, it probably, as a general rule, is limited to the surface-soil, as it is only there the conditions for obtaining circulation of air are sufficiently favourable. A great deal, of course, will depend on the nature of the soil—i.e., as to its texture. In a clayey subsoil the principal hindrance to nitrification will be the difficulty of obtaining sufficient aeration. In clay soils it is probable, therefore, that nearly all the nitrification goes on in the surface layer; in sandy soils it may take place to a greater depth.[119]

Action of Plant-roots in promoting Nitrification.

In this connection the action of plant-roots in permitting a more abundant access of air to the lower layers of the soil, and thus promoting nitrification, is worth noticing. This has been observed in the case of different crops. Thus the action of nitrification has been found to be more marked in the lower layers of a soil on which a leguminous crop was growing than on that on which a gramineous. "The conditions which would favour nitrification in the subsoil are such as would enable air to penetrate it, as artificial drainage, a dry season, the growth of a luxuriant crop causing much evaporation of the water in the soil. Such conditions, by removing the water that fills the pores of the subsoil, will cause the air to penetrate more or less deeply and render nitrification possible. Subsoil nitrification will thus be most active in the drier periods of the year" (Warington).

Nature of Substances capable of Nitrification.

What kinds of nitrogenous substances are capable of undergoing this process of nitrification are not yet well known. The question is, of course, one of great importance, as the rapidity with which a nitrogenous body nitrifies will be an important factor in determining its value as a manure. Unfortunately, on this subject we know, as yet, very little. We are well aware that the nitrogen present in the humic matter of the soil is readily nitrifiable. In the experiments on nitrification the nitrogenous bodies used have been chiefly ammonia salts, so that it is difficult to say whether, in the case of other nitrogenous substances, micro-organic life of a different sort has not also been active and has converted the nitrogen into ammonia, and thereby prepared the way for the process of nitrification.

That various manures, such as bones, horn, wool, and rape-cake are readily nitrifiable, has been shown by experiment. Laboratory experiments have also been carried out on such different nitrogenous substances as ethylamine, thiocyanates, gelatin, urea, asparagin, and albuminoids of milk. But in all these experiments, how far these bodies have been directly acted upon by the nitrifying organisms, or how far they have first undergone a preparatory change in which their nitrogen has been first converted into ammonia, is impossible to say. It is at least quite probable that all the organic forms of nitrogen have first to be converted into ammonia ere they are nitrified.

Rate at which Nitrification takes place.

A question which is practically of no little importance is the rate at which nitrification takes place. From what has been already said as to the nature of the conditions favourable for the process, it will be at once seen that this will depend on how far these conditions are present in the soil. In point of fact the rate at which nitrification takes place will vary very much in different soils. A greater difference, however, in the rate at which it takes place, will be found even in the same soils at different periods of the year. In this country, where the most favourable temperature for its development is seldom reached, it never goes on at the same rate as in tropical climates. One of the causes of the greater fertility of tropical soils is due, doubtless, to the very much longer duration of the period of nitrification, as well as to its greater intensity. As, however, temperature is not the only condition, and the presence of moisture is quite as necessary, it may be that its development is seriously retarded in many tropical climates by the extreme dryness of the soil during long periods.

Takes place chiefly during the Summer Months.

Although in this climate, as has already been pointed out, nitrification probably goes on during most of the winter months, owing to the fact that the temperature of our soils is only occasionally below the minimum temperature at which the process takes place, yet there can be little doubt that the great bulk of the soil-nitrates are produced during a few months in summer. A fair conception of this amount is afforded by the interesting experiments on the composition of drainage-waters made at Rothamsted, which we shall have occasion to refer to immediately. It may be pointed out, however, that it is not always safe to take the amount of nitrates found in drainage-waters as an infallible indication of this rate, for this amount will depend to a certain extent on the amount of rainfall, and would be misleading in the case of a long period of drought. On the whole, however, it furnishes us with extremely useful data for the elucidation of this important problem.

Process goes on most quickly in Fallow Fields.

It has been shown in the Rothamsted experiments that the process goes on best in fields lying in bare fallow; and in this fact lies the explanation of one of the many reasons why the practice of leaving fields in bare fallow, so common in past times, and still practised in the case of clay soils in some parts of the country, was so beneficial to the land thus treated. But despite this fact, the practice of leaving soils in bare fallow can scarcely be justified from this point of view, as the loss of nitrates through the action of rain is very great in our moist climate.

Laboratory Experiments on Rate of Nitrification.

Several interesting experiments have been carried out with the object of affording data for estimating the rate at which the process may go on in our soils under certain conditions. An old experiment, carried out by Boussingault, illustrates, in a general way, how rapid the process is under favourable circumstances. A small portion of rich soil was placed on a slab protected by a glass roof, and was moistened from time to time with water. The amount of nitrate of potash formed under these circumstances was estimated from time to time during a period of two months. During the first month (August) the percentage was increased from .01 to .18 (equal to about 5 cwt. of nitrate of potash per acre). The increase during the second month (September) was very much less,—indeed only about a seventh of the amount.[120] The soil experimented with was an extremely rich garden soil, and all the conditions for nitrification were most favourable.

Of recent experiments on the rate of nitrification, the most striking, perhaps, are those by Schloesing. He mixed sulphate of ammonia with a quantity of soil fairly rich in organic matter, and containing 19 per cent of water. During the twelve days of active nitrification no less than 56 parts of nitrogen per million of soil were nitrified per day. Taking the soil to a depth of 9 inches, this would be equal to more than 1 cwt. per acre—an amount of nitrogen equal to that contained in 6 cwt. of commercial nitrate of soda. These experiments are interesting as showing what is probably the maximum rate of nitrification under the most favourable circumstances, and where there is an abundant supply of easily nitrifiable nitrogen. That nitrification ever takes place in our soils to this extent is not to be for a moment supposed.

Warington, in his Rothamsted experiments, has found that the greatest rate, working with ordinary arable soil (first 9 inches) from the Rothamsted farm, was .588 parts per million of air-dried soil per day—i.e., 1.3 lb. per acre (equal to about 8 lb. of nitrate of soda). Similar soil, when supplied with ammonia salts, showed nearly double this quantity. Higher results were obtained by Lawes and Gilbert with rich Manitoba soils, the average rate being .7 parts per million per day.

The last of these interesting laboratory experiments on the rate of nitrification we shall refer to, are those by DehÉrain. He experimented with soils containing different amounts of nitrogen and moisture. With a soil containing .16 per cent of nitrogen he obtained, during a period of 90 days, rates of nitrification varying from .71 to 1.09 per million parts of soil. The maximum quantity was formed when the soil contained 25 per cent of moisture. On a soil considerably richer—viz.,.261 per cent of nitrogen—a higher rate of nitrification took place—1.48 parts per million. The highest rate obtained in these experiments showed, when calculated to pounds per acre, about 5-1/2, taking the soil to a depth of 9 inches. When the soil was alternately dried and moistened the process was most rapid.

Portion of Soil-nitrogen more easily Nitrifiable than the rest.

Lastly, it may be noticed that in the above-cited experiments, and others of a similar kind, the process goes on most rapidly at first, and steadily diminishes thereafter. This is due to the fact, that there is generally a certain quantity of nitrogen in most soils in a more easily nitrifiable condition than the rest, so that when this becomes oxidised nitrification proceeds more slowly. It would further seem that the nitrogen of the subsoil is less easily nitrified than that of the surface-soil.

Rate of Nitrification deduced from Field Experiments.

While the above experiments throw much light on the question of the rate at which nitrification may go on under different circumstances, the results furnished by actual analyses of soils and their drainage-waters are of still more practical value; and the Rothamsted experiments fortunately furnish us with a number of these valuable results.

Quantity of Nitrates formed in the soils of Fallow Fields.

These researches had to be carried out on soil taken from fields lying in bare fallow; for no true estimate of the amount of nitrates formed could have been obtained from cropped fields. In the first 27 inches of soil of six separate fields, nitrate-nitrogen was found to vary from 36.3 lb. to 59.9 lb. per acre. In four of these fields the largest proportion was found in the first 9 inches of soil; in the remaining two, in the second 9 inches; while the third 9 inches in two fields showed almost as large a proportion as the first 9 inches.[121]

Position of Nitrates depends on Season.

The position of nitrates in the soil depends largely on the season; for, as has been already pointed out, their production is almost entirely limited to the surface-soil, and it is only by being washed down in rain that they find their way to the lower layers. A wet season, therefore, has the effect of increasing their percentage in the lower soil-layers.

Nitrates in Drainage-waters.

As there is a certain proportion of nitrates that finds its way even below the first 27 inches of soil, the above results do not show their total production. To accurately estimate this amount we must ascertain the quantity escaping in drainage-water. Here, again, the Rothamsted experiments furnish us with valuable data. The amount found in drainage-waters of course naturally varies very much, and depends largely on the rainfall; but taking an average of twelve years, this has been found to amount to between 30 and 40 lb. per acre—an amount not so very far short of that found in the first 27 inches of the soil itself. This was from comparatively poor soil, it must be remembered, and a much larger quantity would undoubtedly be produced in the case of richer soils. Adding then the results together, we find that in soils like those at Rothamsted, when in bare fallow, between 80 and 90 lb. of nitrogen are converted into nitrates in some fourteen months' time—an amount equal to about 5 cwt. of nitrate of soda. It is a fact of no little practical significance that nearly one-half of this large quantity is found in the drainage-water.

Amount produced at Different Times of the Year.

Some indication of the rate at which nitrification takes place during the different months of the year is obtained from a study of the results of the analyses of drainage-waters which we have just referred to. This, however, it must be remembered, only furnishes us with a very approximate indication. The month showing the greatest amount of nitrates in the drainage-water must not necessarily be regarded as that during which nitrification has been most active, for the amount chiefly depends on the rainfall. In illustration of this it will be found that the drainage-water during the autumn and early winter months contains most nitrates, not because nitrification is most active then, but because the rainfall is greatest, and a large proportion of the nitrates formed during the drier summer months is being only then washed from the soil. The amount of nitrates in drainage-waters steadily diminishes from autumn through the winter months, and is least in spring. The total amount of nitrates found in the drainage-water is, therefore, not a safe guide. What, however, does furnish us with a more reliable indication is the percentage of nitrates in the drainage-water. Regarding the results of the analyses of drainage-water (see Appendix) from this point of view, it will be seen that this is greatest during the month of September, and least during April.[122]

Nitrification of Manures.

A subject which has not yet been specially referred to, but which is of great practical importance, is the nitrification of manurial substances. It is unfortunate that the amount of research hitherto devoted to this important question has been slight, and that the knowledge we possess is therefore very limited.

Ammonia Salts most easily Nitrifiable.

One fact, however, about which there can be little doubt, is that nitrogen in the form of ammonia salts is, of all compounds of nitrogen, the most easily nitrifiable. Indeed, as we have already indicated, it is highly probable that the conversion of the different forms of organic nitrogen into ammonia is an intermediate stage in the nitrification of these bodies. At any rate it seems to be invariably the case that when a mixture of nitrogen compounds, including ammonia salts, are allowed to nitrify, the nitrogen in the form of ammonia is the first to become nitrified.

Sulphate of Ammonia most easily Nitrifiable Manure.

It follows from this that sulphate of ammonia, the most common of ammoniacal manures, is one of the most speedily nitrified when applied to the soil. The rate at which the nitrification of this manure takes place naturally varies according to the quantity applied, and other circumstances, such as the nature of the soil and the weather, &c. That, under favourable circumstances, the conversion of ammonia into nitrates is very rapid, has been shown by a number of experiments. DehÉrain has found that when sulphate of ammonia was mixed with soil at the rate of 2 cwt. per acre, nitrification took place at the rate of 1/100th of its nitrogen per day.

Rate of Nitrification of other Manures.

Of other nitrogenous manures, guano, it would seem, comes next to sulphate of ammonia in the rate at which it becomes nitrified in the soil; while next to guano stand green manures, dried blood, meat-meal, &c. As we should expect, such a manure as shoddy is very slowly nitrified. The rate at which the nitrogen compounds in farmyard manure become nitrified, when incorporated with the soil, vary very much according to circumstances. It goes on probably at a greater rate than the ordinary nitrification of soil-nitrogen. It is a somewhat striking fact that the effect of adding nitrate of soda to the soil may be at first to check nitrification. That the addition of common salt, even in small quantities, has this result, is at any rate certain. The presence of salt to the extent of one-thousandth of the weight of the soil, has a prejudicial effect.

Soils best suited for Nitrification.

To recapitulate, then, nitrification is effected through the agency of micro-organisms, which are present to a greater or less extent in all soils. It requires for its favourable development air, warmth, moisture, absence of strong light, presence of a salifiable base—viz., carbonate of lime—the presence of certain mineral food-constituents, such as phosphates, and a certain amount of alkalinity. It consequently takes place to the least extent in barren sandy soils. Soils rich, light, well ventilated, uniformly moist, warm, and chalky, are best suited for its development. Other things being equal, it develops better in a fine-grained soil than in a coarse-grained soil, because, in the case of the former, aeration and uniform moistening of the soil are best secured.

Absence of Nitrification in Forest-soils.

A point of considerable interest is the practical absence of the process in forest-soils. The absence, or occurrence in the most minute traces, of nitrates in forest-soils has been accounted for by the lowness of the normal temperature of such soils and their extreme dryness. This latter condition is accounted for by the enormous transpiration of water which takes place through the trees, especially in summer-time, which is such as to render the soil almost air-dry. Lastly, it may be accounted for by the want of mineral food ingredients.

Important Bearing of Nitrification on Agricultural Practice.

Before concluding this chapter, it may be well to draw attention to the important bearing which nitrification has on agricultural practice. The light which our present knowledge—imperfect as it is—of this most interesting process throws on the theory of the rotation of crops is very striking, for it shows how the adoption of a skilful rotation may be made to prevent the loss of enormous quantities of the most valuable of all our soil-constituents,—the one on the presence of which fertility may be said most to depend—viz., nitrogen.

Desirable to have Soil covered with Vegetation.

The constant production of nitrates going on in the soil, the inability of the soil to retain them, and the consequent risk of their being removed in drainage, furnish a strong argument in favour of keeping our soils as constantly covered with vegetation as possible.

Permanent Pasture most Economical Condition of Soil.

From the point of view of conservation of soil-nitrates, permanent pasture may be said to be the most economical condition for the soil to be in. In such a case the nitrates are assimilated as they are formed, and, by being converted in the plant into organic nitrogen, they are at once removed from all risk of loss. A consideration, therefore, of the process of nitrification furnishes many arguments in favour of laying down land in permanent pasture—a practice which of late years has been increasingly followed in many parts of the country. As, however, it is not possible or desirable to carry out this practice beyond certain limits, the rotation which most nearly conforms to the condition of keeping the soil covered with vegetation, and most approximates in this respect to permanent pasture, is most to be recommended.

Nitrification and Rotation of Crops.

The chief risk of loss of nitrates is in connection with a cereal crop such as wheat. Where turnips follow wheat, there is a period during which the soil is left uncovered, and during which most serious loss of nitrates is apt to ensue. The risk of loss is enhanced by the fact that the assimilation of nitrates by cereals ceases before the season of their maximum production in the soil. The soil is then left bare of vegetation during the autumn, which is the most critical period of all, and the result must be serious loss. In order to minimise this loss, the practice of growing catch-crops has been had recourse to. As, however, this practice will be dealt with elsewhere, nothing further need here be said.

FOOTNOTES:

[97] As the formation of nitrites is a stage in the process, the term nitrification includes the formation of nitrites as well as nitrates.

[98] Nitre seems to have been known as early as the thirteenth century.

[99] Lawes and Gilbert, for example, have shown that in the Rothamsted soils it only amounts to a few parts per million of soil.

[100] See Appendix, Note I., p. 196.

[101] The artificial production of nitre seems to have been first effected by Glauber in the seventeenth century.

[102] The lime-rubbish from old buildings, especially those parts which have come in contact with the earth, or plastering from the walls of damp cellars, barns, stables, &c., have been found to be rich in nitrate of lime, and, as has been long well known, constitute by themselves a valuable manure. The formation of the nitrate of lime can be accounted for by the contact of the lime with nitrogenous matter of different kinds.

[103] As much of the nitric acid in this solution was present as nitrate of lime, it was usually treated with a solution of potassium carbonate, the result being the precipitation of the lime as carbonate, pure saltpetre being left in solution, according to the following equation—

K2CO3 + Ca(NO3)2 = 2 KNO3 + CaCO3.

Under the French mode of manufacture, the process was considered to have developed satisfactorily when 1000 lb. of earth, at the expiration of two years, yielded 5 lb. of nitre.

[104] Pasteur had already in 1862 expressed the opinion that nitrification might probably be in some way connected with ferments. A. MÜller (see 'Journal of Chemical Society,' 1879, p. 249) was the first to advance the opinion that nitrification was due to the action of a ferment. This conclusion he was led to by the observation that while the ammonia in sewage was converted into nitric acid, no change took place in solutions of ammonia or urine prepared in the laboratory.

[105] Bisulphide of carbon and phenol (carbolic acid) have also been experimented with in connection with their antiseptic action on nitrification. In these experiments the former had a similar effect to chloroform; the phenol, however, while hindering it did not entirely suspend it, due probably to the difficulty of bringing the phenol vapour into thorough contact with the soil-particles.

[106] Winogradsky has named the nitrous organism nitrosomonas, and the nitric organism nitrobaeter.

[107] From a series of Lectures delivered by him in connection with Lawes Agricultural Trust, in the United States.

[108] This silica-jelly consists of dialysed silicic acid, ammonium sulphate, potassium phosphate, magnesium sulphate, calcium chloride, and magnesium carbonate.

[109] This fact is all the more striking when we remember that this decomposition of carbonic acid is best effected in the dark, since light is prejudicial to nitrification.

[110] See Appendix, Note II., p. 196, and Note III., p. 197.

[111] See Appendix, Note V., p. 198.

[112] This is shown by the fact that nitrification will only continue in a solution of carbonate of ammonia till one-half the ammonia is nitrified. It then stops. The base, with which the nitrous acid combines as it is formed, being at that stage entirely used up, nitrification is no longer possible. With regard to urine solutions the same is the case. Nitrification thus will only take place where there is a sufficiency of base.

[113] See Appendix, Note IV., p. 197.

[114] It would seem that an alkalinity much exceeding four parts of nitrogen per million is prejudicial to the process.

[115] According to Warington, solutions containing 50 per cent of urine become nitrifiable when sufficient gypsum is added. The gypsum neutralises the alkalinity of nitrifying solutions by converting the alkaline ammonium carbonate into neutral ammonium sulphate, the calcium carbonate being precipitated.

[116] See Chapter on Farmyard Manure.

[117] As practically illustrating this fact, a solution kept at 10° C. required ten days, while a solution kept at 30° C. required only eight days for nitrification.

[118] In sixty-nine trials no failure to produce nitrification by seeding with soil from a depth, of 2 feet was experienced. Similarly in eleven trials only one failure took place with soil from a depth of 3 feet. With clay soil from a depth of 6 feet success took place to the extent of 50 per cent. No nitrification was obtained with clay from a depth of 8 feet. Entire failure was experienced with chalk subsoil. The process thus diminishes in activity the lower down we go.

[119] Koch has found that in soils he has examined few organisms were found at a depth below 3 feet.

[120] See Appendix, Note VI., p. 198.

[121] For full analytical results see Appendix, Note VII., p. 198.

[122] We find the least amount in the month of April. In the water, from a 20-and 60-inch gauge respectively, the amounts were 1.35 lb. and 1.61 lb. per acre (rainfall 2.25 inches). From then on to November the amount steadily increases. In the latter month it reaches its maximum—viz., 6.50 lb. (20-inch gauge) and 5.98 lb. (60-inch gauge) per acre (rainfall 2.30 inches). See Appendix to Chapter III., Note VIII, p. 160.


                                                                                                                                                                                                                                                                                                           

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