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 6-1/2 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.