Chapter XVIII: Part I: Historical Introduction (2)

While the relation of free nitrogen to the plant has long been, and still is, a very obscure problem, it was early recognised that the combined nitrogen present in soils and manures was an important source of plant-food. Reference has already been made to the early theory of Sir Kenelm Digby regarding the value of nitrates.[28] De Saussure, as we have also already seen, was fully impressed with the importance of applying nitrogen to the soil as a manure. Liebig's early attitude on this question was to the effect, that to apply nitrogen in manures was quite unnecessary, as the plant had a sufficient source in the ammonia present in the air, which he erroneously supposed was sufficient in quantity to supply all the needs of the crops. Despite this early recognition of the value of combined nitrogen to the plant, it is only of recent years that we have obtained any definite knowledge as to the respective value of its different compounds as manures, or as to the form in which it is assimilated by the plant. It exists in three forms--(1) as organic nitrogen; (2) as ammonia salts; (3) as nitrates and nitrites. Much experimental work has during late years been devoted to studying the comparative action and merits of these three forms.

_Relation of Organic Nitrogen to the Plant._

First, as to the relation of organic nitrogen to the plant. There is a large number of different organic compounds which contain nitrogen. That the plant is able to assimilate certain of these organic compounds, seems, from several experiments, to be extremely probable. From certain researches, carried out as far back as the year 1857, Sir Charles Cameron concluded that the plant could assimilate one of them--viz., _urea_. From what, however, we have subsequently learned regarding the process of "nitrification," it is quite probable that the nitrogen in these experiments was first converted into nitrates before being assimilated. At any rate, as the plants were not tested for urea, the experiments must be regarded as leaving the problem unsolved.

Other experiments were carried out of a similar nature by Professor S. W. Johnson, the different kinds of nitrogen experimented with being _uric acid_, _hippuric acid_, and _guanine_. But here, again, no definite conclusion can be drawn, as no analyses were made of the plants. More recently, however, Dr Hampe has carried out experiments with _urea_, _uric acid_, _hippuric acid_, and _glycocoll_. These experiments may be held as demonstrating the fact that at least one organic compound of nitrogen is capable of being assimilated, as urea was actually identified as being present in the plants experimented with. From further experiments, carried out by Dr Paul Wagner and Wolff, _glycin_, _tyrosin_, and _kreatin_ are able to be assimilated by the plant.

_Plants able to absorb certain Forms of Organic Nitrogen._

We may conclude, then, from these interesting experiments, that plants are able to absorb certain organic forms of nitrogen. That they do so in nature to any extent is extremely improbable, such organic forms of nitrogen being rarely present in the soil, or if present, being converted into ammonia or nitrate salts before assimilation.

_Nature of Humus in the Soil._

While on the subject of organic nitrogen, reference may be briefly made to that substance known as _humus_,--the name applied to the organic portion of soils,--a substance which figures so largely in early theories of plant-nutrition. The most elaborate investigation of the composition of humus has been carried out by Mulder. According to Mulder, it is composed of a number of organic bodies, and he has identified the following substances--ulmin, humin, ulmic, humic, geic acids, &c. These bodies are composed of carbon, hydrogen, and oxygen, which are invariably associated with nitrogen. Detmer and Simon have further investigated the subject. The true function of humus, it would seem, in addition to its numerous mechanical properties, is to furnish, by its decomposition, carbonic acid and nitrogen--in the form of ammonia and nitric acid--to the soil; the former acting as a solvent of the mineral food, the latter as the source of the plant's nitrogen. The old theory, therefore, that the presence of humus in a soil is a condition of fertility, is not so far removed from the truth. Where there is an abundance of humus in the soil there is likely also to be an abundance of nitrogen.

_Relation of Ammonia to the Plant._

It seems to be beyond doubt that nitrogen is directly absorbed by plants in the form of ammonia. Liebig, as we have seen, concluded that this was the great source of nitrogen for the plant, and that the ammonia compounds present in the air were an all-sufficient supply. Subsequent research, while confirming his belief so far as regards the capability of plants to assimilate nitrogen in the form of ammonia, has proved that the amount of ammonia present in the air is very minute, and utterly inadequate to supply the plant with the whole of its nitrogen. Investigations have been made on this subject by Graeger, Fresenius, Pierre, Bineau, and Ville. According to Ville's researches, which are among the most recent, the amount does not exceed 30 _parts per thousand million parts of air_.[29] Some conception of the value of this source of nitrogen may be gained by estimating the quantity falling, dissolved in rain, on an acre of soil throughout the year. Various estimations of the total amount of combined nitrogen, which is in this way brought to the soil, have been made. A certain amount of discrepancy, it is true, is to be found in these various estimations, no doubt largely due to the difference in the circumstances under which the investigations were carried out. Mr Warington has made several investigations at Rothamsted, and, according to his most recently published figures, the total quantity only amounts to 3.37 lb. per acre per annum--of which only 2.53 lb. is as ammonia itself.[30]

As already mentioned, there can be little doubt that plants can absorb nitrogen in the form of ammonia. The question of how far plant-leaves are able to absorb ammonia is a much debated one. It is probable that if they can do so, it is only to a very small extent.[31] The question as to whether the plant's roots can absorb ammonia or not, is also a very keenly debated one. The point is a very difficult one to decide, and is much complicated by the consideration that ammonia, when applied to the the soil, is so speedily converted into nitric acid. Despite, however, these difficulties, and the vast amount of controversy on the point, the experiments of Ville, Hosaeus and Lehmann, seem to indicate beyond doubt that ammonia is a direct source of nitrogen. Lehmann's experiments would seem, further, to indicate that there are certain periods of a plant's growth when its preference for ammonia salts seems to be greater than at other times. The point, however, it must be confessed, is still an obscure one. The great difficulty in deciding it, as has just been said, lies in the fact that ammonia salts, when applied to a soil, are, by the process of nitrification, converted into nitrates. In experimenting, therefore, with ammonia, and noting the results, it is wellnigh impossible to say, except by subsequent analyses, whether the nitrogen in the ammonia salts has not been converted into nitrates before assimilation.

_Relation of Nitric Acid to the Plant._

Thirdly, as to nitrogen in the form of nitrates. While it is true that plants can absorb nitrogen in certain organic forms and as ammonia salts, it is now a well-known fact that the chief, and by far the most important, source of nitrogen is nitric acid. Probably more than 90 per cent of the nitrogen absorbed by green-leaved plants from the soil is absorbed as nitrates. The tendency of all nitrogen compounds in the soil is towards conversion into nitric acid. It is the final form of nitrogen in the soil. The precise method in which this conversion takes place is a discovery of only a few years' standing. The great economic importance of this discovery, made by the French chemists Schloesing and Muentz, and associated in this country with the names of Warington, Munro, and P. F. Frankland, is only gradually being appreciated. It is without doubt one of the most interesting made in the domain of agricultural chemistry of late years.

_Nitrification._

It was in the year 1877 that the two French chemists above referred to published the results of some experiments they had carried out, which proved that nitrification--the name given to the process by which ammonia or other nitrogen salts are converted in the soil into nitric acid--was due to the action of micro-organic life.

The basis of the theory rests upon the fact that dilute solutions of ammonia salts or urine, containing all the necessary constituents of plant-food, if previously sterilised, may be kept for an indefinitely long period of time, provided the air supplied be filtered through cotton wool,--so as to prevent the entrance of micro-organisms--without any formation of nitrates. Introduce, however, into such a solution a little fresh soil, and nitrification will soon follow.

The conditions under which the nitrification ferment acts, as well as the nature of the ferment, or rather ferments, have subsequently been carefully studied by Schloesing and Muentz, Winogradsy, Deherain, Kellner, and other Continental observers, and especially by Warington, Munro, and P. F. Frankland in this country. These conditions cannot be gone into here. They will be fully discussed in the chapter on Nitrification. Briefly stated, they are a certain range of temperature (between slightly above freezing-point and 50 deg. C., the maximum activity taking place, according to Schloesing and Muentz, at about 30 deg. C.); a plentiful supply of atmosphere oxygen (hence the fact observed by Warington, that nitrification is chiefly limited to the surface-soil); a certain amount of moisture; and the presence of certain of the necessary mineral plant constituents, and the presence of carbonate of lime.

The light which these discoveries throw upon the extremely complicated question of the fertility of the soil is considerable, as it follows that no soil can be regarded as really a fertile one in which the process of nitrification does not freely take place. They furthermore explain many facts, hitherto observed but not well understood, with regard to the action of different nitrogenous manures.

_Ash Constituents of the Plant._

We now come to consider the present state of our knowledge on the essentialness of the ash or mineral portion of the plant. While a portion of the plant's substance which, up to Liebig's time, had obtained little notice, it has, since the publication of his famous "mineral" theory, obtained an ever-increasing amount of investigation.

Up till 1800 practically nothing was known of the function of the ash constituents. In 1802 de Saussure wrote that it was unknown whether the constituents of many plants were due to the soils on which they grew, or whether they were the products of vegetable growth. Some two years later, however, he was enabled to carry out a number of experiments which really placed the subject on a firm scientific basis. The essentialness of the ash constituents was only, however, placed beyond all doubt by Wiegmann and Polstorff's researches, carried out in 1840.

Reference has already been made to the great stimulus given to research by the promulgation of Liebig's mineral theory.

_Methods of Research._

In epitomising the vast amount of work carried on since 1840, with the view of ascertaining the essentialness of the various substances found in the ash of plants, two methods of experimentation have been followed.

_Artificial Soils._

The first of these two methods was that adopted in the famous experiments, carried out by Prince Salm-Horstmar, which have done so much to further our knowledge on this question. It consisted in growing plants on an artificial soil--formed out of sugar-charcoal, pulverised quartz or purified sand--to which were added the different food constituents.

_Water-culture._

While the results obtained by Prince Salm-Horstmar by this method were of a most valuable nature, subsequent experimenters have abandoned his method for the other method--viz., "water-culture." The medium used in this process is pure water; and it is from experiments carried out in water-culture that much of our present knowledge, in regard to the relation of the ash constituents to the plant, is due.

The names of those who have worked in this department are very numerous. Among them may be mentioned Knop, Sachs, Stohmann, Nobbe, Rautenberg, Kuehn, Lucanus, W. Wolff, Hampe, Beyer, E. Wolff, P. Wagner, Bretschneider and Lehmann. The results obtained by these and other experimenters have demonstrated the following facts.

The substances which have been found in the ash of plants are: _potash_, _soda_, _lime_, _magnesia_, _oxide of iron_, _oxide of manganese_, _phosphoric acid_, _sulphuric acid_, _silica_, _carbonic acid_, _chlorine_, _lithia_, _rubidia_, _alumina_, _oxide of copper_, _bromine_, _iodine_, and occasionally even other substances. Of these, however, only six are probably absolutely necessary for plant-growth--viz., _potash_, _lime_, _magnesia_, _oxide of iron_, _phosphoric acid_, and _sulphuric acid_. Three other substances seem also to be almost invariably present, and may possibly be essential--in very minute quantities at any rate--viz., _chlorine_, _soda_, and _silica_. With regard to _alumina_ and _oxide of copper_, these constituents must be regarded as accidental; while _iodine_ and _bromine_ only occur in the ash of marine plants.

_Method of Absorption of Plant-food._

A department of vegetable physiology which has had much work devoted to it is the method in which plant-roots absorb their food. The plant's nourishment is absorbed in solution by means of the roots. Its absorption takes place, according to Fischer and Dutrochet, who have investigated the subject at great length, by the process known as _endosmosis_. It has also been established by numerous experiments, that different plants require different constituents in different proportions.

_Water as a Carrier of Plant-food._

The function performed by water, as the carrier of plant-food, and the motion of the sap of the plant, are questions which have also received much attention. The motion of the plant's sap seems to have attracted a great deal of attention at a very early stage of the study of plant physiology. As far back as 1679, Marriotte studied it. Among other old experimenters were Hales, Guettard, Senebier, Saint-Martin, de Candolle, and Miguel. In more recent times, it has been investigated by Schuebler, Lawes and Gilbert, Knop, Sachs, Unger, and Hosaeus. Some idea of the enormous amount of water transpired by plant-leaves may be gained by the statement that from 233 lb. to 912 lb. of water are transpired for every pound of plant-tissue formed.[32]

_Agronomy._

When we come to deal with questions relating to the chemistry of the soil, we find that so much investigation has been devoted to this one branch of agricultural chemistry as to constitute it a special branch by itself--known in France under the name of _agronomie_--and being taught in the large agricultural colleges by special professors of the subject. The value of studying the properties of soils was recognised at an early period. This study was for long largely confined to their _physical_, or, what are popularly known as their _mechanical_ properties. Thus Sir Humphry Davy ascertained many important facts with regard to the heat and water absorbing and retaining properties of soils.

_Retention by Soil of Plant-food._

It was not till a later period that the power soils possess of fixing from their watery solutions various plant-foods, both organic and inorganic, was discovered. The earliest recognition of this most important property of soils was made by Gazzeri, who, in 1819, called attention to the fact that the dark fluid portion of farmyard manure was purified on passing through clay. He concluded that soils, more especially clayey soils, possessed the property of being able to fix from their watery solutions the necessary plant-food constituents, and fix them beyond risk of loss, only affording a gradual supply to the plant as required.

The first experiments carried out on this subject were those by Huxtable and Thompson in 1850. The liquid portion of farmyard manure was filtered through soil and subsequently examined, when it was found to have not only lost its colour, but also to have lost its smell. Ammonia and ammonia salts were also experimented with, and it was found that soils possessed the power of fixing ammonia.

To Thomas Way, however, we are indebted for the most valuable contribution on this important subject made by any one single investigator. His experiments were not merely carried out with regard to ammonia, but also with regard to other bases--such as potash, lime, magnesia, soda, &c. Since Way's experiments much work has been done by Liebig, Stohmann, Henneberg, and Heiden, as also by Voelcker, Eichhorn, Knop, Rautenberg, Pochwissnew, Warington, Beyer, Bretschneider, Sestini, Laskowsky, Strehl, Pillnitz, Peters, W. Wolff, Lehmann, and Biedermann.

_Bases and Acids fixed by Soil._

From these experiments it may be taken as proved beyond doubt that soils have the power of fixing, to a greater or less extent, the following bases: ammonia, potash, lime, magnesia and soda; as well as the two acids, phosphoric and silicic. The order in which the different bases are fixed is an important point. It would seem that the soil has a greater affinity for the more valuable manurial substances, such as ammonia, potash, and lime, and that these substances are first fixed. That in fixing any one of the above-mentioned bases from its solution, it can only do so at the expense of another base. Thus, in fixing potash, either lime, magnesia, or soda must be given up. Further, when a base in solution, as sulphate or chloride, is absorbed by a soil, the base is alone fixed, while the sulphuric acid or chlorine is left in solution. Lastly, the amount of base absorbed by a soil depends on the concentration of its solution, on the nature of its combination, and the temperature. Way found in his experiments that a clay soil has more power than a peaty soil, and that a peaty soil has more power than a sandy soil.

_Causes of this Fixation._

So much for the fact of soil absorption; as to the cause or causes of this absorption, a great number of theories have been put forward. Those may be divided into two classes--those accounting for it as due to physical properties of the soil; and those, on the other hand, explaining it as due to chemical action.

To the latter class Way's belonged. He explained it as due to the formation in the soil of hydrated double silicates, consisting of a silicate of alumina, along with a silicate of the base fixed. Bruestlein and Peters, on the other hand, were of the opinion that it was purely physical in its nature. A theory has been advanced that it is due to the formation of insoluble ulmates and humates, formed by the union of ulmic and humic acids, along with the bases fixed. Among others who devoted investigation to this interesting question, may be mentioned Rautenberg and Heiden.

On reviewing the evidence, it seems to be pretty well established that it really is mainly a chemical act, due chiefly to the formation of double silicates, and doubtless to a certain extent to the formation of insoluble humates and ulmates. Heiden's experiments would seem to indicate, however, that it is also partly of a physical nature.

With regard to the absorption of phosphoric acid, this has been shown to be a chemical act, and depends on the formation of insoluble phosphates of calcium, iron, aluminium, and magnesium, the percentage of iron especially determining this.

Much analytical work has been accomplished of late years with a view of ascertaining the amount of ash in different kinds of plants, and in the different parts of the plant.

_Action of Manures._

The department of agricultural chemistry which has been most largely developed of late years is that connected with the problems of _manuring_. It is, from a practical point of view, of most value. It is some considerable time since we have recognised that the only three ingredients it is, as a rule, expedient to apply as artificial manures, are _nitrogen_, _phosphoric acid_, and _potash_. The nature, mode of action of the different compounds, and properties of these three substances, and their comparative influence in fostering plant-growth, together with the economic question of which form is, under various circumstances, the most economical for the farmer to use, have together given rise to a large number of "field" and "pot" experiments. As the principles underlying this practice form the subject of the following treatise, any further discussion of the question must be left to the following chapters.

_Note._--The reader interested in the historical development of
agricultural chemistry is referred to Sir J. H. Gilbert's
Presidential Address to the Chemical Section of the British
Association, 1880.

FOOTNOTES:

[1] The History of the Chemical Elements. By Sir Henry E. Roscoe, F.R.S. (Wm. Collins, Sons, & Co.)

[2] Van Helmont's science was, however, of an extremely rudimentary nature, as may be evidenced by the belief he entertained that the smells which arise from the bottom of morasses produce frogs, slugs, leeches, and other things; as well as by the following recipe which he gave for the production of a pot of mice: "Press a dirty shirt into the orifice of a vessel containing a little corn, after about twenty-one days the ferment proceeding from the dirty shirt, modified by the odour of the corn, effects a transmutation of the wheat into mice." The crowning point in this recipe, however, lay in the fact that he asserted that he had himself witnessed the fact, and, as an interesting and corroborative detail, he added that the mice were born full-grown. See 'Louis Pasteur: His Life and Labours.' By his Son-in-law. Translated by Lady Claud Hamilton. (Longmans, Green, & Co.) P. 89.

[3] He then goes on to relate a number of experiments by Cornelius Drebel and Albertus Magnus, showing the refreshing power of this balsam, and then those of Quercitan with roses and other flowers, and his own with nettles.

[4] Priestley, however, did not realise that _carbonic acid gas_ was a necessary plant-food; on the contrary, he considered it to have a deleterious action on plant-growth. Percival was really the first to point out that carbonic acid gas was a plant-food.

[5] It is recorded as an instance of the scientific enthusiasm of the man, that he was wont to carry about with him bottles containing oxygen, which he had obtained from cabbage-leaves, as also coils of iron wire, with which he could illustrate the brilliant combustion which ensued on burning the latter in oxygen gas.

[6] For a full account of Senebier's researches, see 'Physiologie vegetale, contenant une description des organes des plantes, et une exposition des phenomenes produits par leur organisation, par Jean Senebier.' (5 tomes. Geneve, 1800.)

[7] How Crops Grow. By Professor S. W. Johnson. Macmillan & Co. (Introduction, p. 4.)

[8] See p. 40 to 45.

[9] Elements of Agricultural Chemistry, in a course of Lectures for the Board of Agriculture. By Sir Humphry Davy. (London, 1831.)

[10] This department of agricultural research was subsequently carried on by Sprengel, Schuebler, and others.

[11] Born in Paris, 1802; died 11th May 1887.

[12] See p. 40.

[13] While much of Boussingault's work was carried out previous to the year 1840, he continued to enrich agricultural chemistry with numerous valuable contributions up till the time of his death. It may be well here to mention the names of his most important contributions to agricultural science, made subsequent to 1840.

In 1843 he published, in a work entitled 'Economie Rurale,' the results of his numerous experiments and researches. This work is well known to English agriculturists from an English translation which appeared in 1845 (Boussingault's 'Rural Economy,' translated by G. Law. H. Balliere, London).

In 1860 appeared the first volume of his last great work, 'Agronomie Chimie Agricole et Physiologie' This work, which consisted of seven volumes, was not finished till 1884. He died on the 11th of May 1887. It may be added that the Royal Society of London awarded him the Copley medal in 1887.

[14] See British Association Proceedings, 1880, p. 511.

[15] It may be pointed out that, while the amount of ammonia washed down by the rain is small, Schloesing has found in some recent experiments that a damp soil may absorb from the air in the course of a year 38 lb. of combined nitrogen, chiefly ammonia, per acre. See p. 132.

[16] The example, set by Germany, has been followed by other countries in which well-equipped research stations now exist. Perhaps the most striking example of the rapid development of the means of agricultural research is furnished by the United States of America. At present over fifty agricultural experiment stations, more or less well equipped, exist at present in that country, all liberally supplied by State aid. The earliest to be founded, it may be added, was that at Middletown, Connecticut, the date of its institution being 1875.

[17] It may thus claim to be the second oldest experimental station, that instituted by Boussingault at Bechelbronn in Alsace being the oldest.

[18] For an account of the Rothamsted experiments, and a short biography of Sir John Lawes, the reader is referred to a pamphlet by the present writer, entitled 'Sir J. B. Lawes, Bart., LL.D., F.R.S., and the Rothamsted Experiments' ('Scottish Farmer' Office, 93 Hope Street, Glasgow).

[19] Of these numerous elaborate experiments, perhaps those which have attracted the most widespread interest amongst agriculturists have been those carried out on the growth of wheat on the same land year after year for a period of nearly fifty years. The important light which this series of experiments has thrown upon the theory of the rotation of crops, and the subject of the manuring of cereals, is very great.

[20] Associated in some cases with phosphorus and sulphur.

[21] It must be pointed out that plant-respiration does not take place _only_ during the night-time. It probably goes on at all times, but it is only during the night-time that its action is apparent, as the reverse process of carbon assimilation, which goes on at an incomparably greater rate, masks its action during the daytime.

[22] The length of the day has an important influence on plant-growth, as is evidenced by the rapid growth of vegetation in Norway and Sweden. In these countries there is a late spring, and a short and by no means hot summer, but a very long period of daylight.

[23] A point of great interest which these experiments elucidated is that nocturnal repose is not absolutely necessary for the growth and development of all plants.

[24] See pp. 15 and 22.

[25] See p. 22.

[26] See Chapter III., pp. 120 and 131.

[27] Further reference is made to this subject in Chapter III., p. 136.

[28] See p. 6.

[29] See Phil. Trans., Part II., 1861, pp. 444-446. Lawes & Gilbert. Schloesing has found in the air in the neighbourhood of Paris 1 lb. of ammonia in 26,000,000 cubic yards; while Muentz found only about half that amount in a similar quantity of air on the top of the Pic du Midi.

[30] See Chapter III., pp. 119, 120; Appendix, p. 155.

[31] Some recent experiments by Dyer and Smetham would seem to show that comparatively small quantities of ammonia in the air prove actually hurtful to plant-life. Thus they found that one volume of ammonia in 1000 volumes of air was fatal to hardy plants; while one volume in 3000 volumes killed tender ones.

[32] According to the experiments of Hellriegel and Wollny. The quantity, it may be added, varies with the leaf-surface and the length of the period of growth of the plant. It is greatest with clovers and grasses, and least in the potatoes and roots.