Barium.—From solution of barium bearing minerals in hydrofluosilicic acid fragments, no characteristic crystals, are obtained. Treated with hydrofluoric and sulfuric acids the barium is left as sulfate. If this salt be dissolved in boiling oil of vitriol and a drop of the solution placed on the slide, a mixture of rectangular tablets and St. Andrew’s cross-shaped growths will be separated before any crystals of gypsum which may be present appear. When strontium is present, the barium sulfate residue obtained by treatment with hydrofluoric and sulfuric acids should be fused with sodium and potassium carbonate, washed with water until the sulfuric acid is removed, the residue dissolved in hydrochloric or nitric acids, and the solution treated with potassium chromate. Pale yellow crystals of barium chromate are thus obtained, which resemble in form those secured by dissolving the barium sulfate in oil of vitriol. Strontium is not precipitated by this treatment. If potassium ferrocyanid be used instead of barium chromate with the hydrochloric acid solution, crystals of barium potassium ferrocyanid are formed of a bright yellow color and rhombohedric shape.

Strontium.—From a hydrofluosilicic acid solution, strontium crystallizes in columns or tablets of the monoclinic system as strontium silicofluorid, SrSiF₆. On treating these with sulfuric acid, rhombic plates of strontium sulfate are formed, which serve to distinguish this element from calcium. On treatment of the particles of the original mineral with hydrofluoric and sulfuric acids, the strontium remains in the insoluble residue. When this residue is treated with boiling oil of vitriol, rhombic plates of celestine are separated. If the residues above mentioned be dissolved by fusion with the alkaline carbonates, washed with water, dissolved in hydrochloric acid and treated with oxalic acid, octahedral crystals of strontium oxalate are formed.

Iron.—Mineral particles containing iron give crystals, when treated as is first described above, which are fully isomorphous with those obtained from magnesium. By moistening the crystalline mass with potassium ferrocyanid, the presence of iron is at once revealed by the blue coloration produced.

Aluminum.—No crystals containing aluminum are formed from the mineral particles containing this substance when dissolved in the solvent already mentioned. If, however, the gelatinous mass be dissolved in a little sulfuric acid and a fragment of a cesium salt added, beautiful crystals of cesium alum are obtained, illustrated in Fig. 53.

Phosphorus.—When a mineral fragment containing phosphorus is treated according to the usual analytical methods for securing the ammonium magnesium phosphate, crystals are obtained of the form shown in Figs. 54 and 55. A phosphatic fragment of silt may be identified when soluble by treatment with nitric acid and ammonium molybdate. On slowly drying, rhombohedral crystals are produced, yellow by reflected, and green by transmitted light. Their form is shown in Fig. 56.

260. Petrographic Examination of Silt Particles.—The larger silt particles and the minute fragments of minerals in the soil can best be studied in thin sections. For this purpose the following plan, proposed by Thoulet, may be used. Mix the soil minerals in considerable proportion—Thoulet recommends ten per cent, but a greater percentage is often better—with zinc oxid and make into a paste with sodium silicate. The paste should be worked to the consistence of putty and then rolled into little tablets about one-eighth of an inch thick and an inch in diameter. After drying a day or two without heating, the tablets become hard enough to mount and grind like rock sections. These tablets are mounted in Canada balsam on glass slides and ground as thin as possible with fine emery on the turn-table or glass plate, as rock sections are treated. As these tablets are not as strong as rock sections usually are, they require care in this treatment. Some of the grains also are apt to be torn out in the process of grinding and to compensate for this loss a number of slides should be prepared with each lot of soil minerals. When this operation has been successful, the optical properties of the various minerals can be studied as in rock sections.

As the iron oxid contained in the soils obscures the transparency of the minerals, it is well to treat a portion of the material under examination with hot hydrochloric acid for a short time to remove this oxid and then prepare slides with the cleansed material and compare results with the untreated. As the acid will dissolve phosphates and carbonates, and will partly or wholly decompose some other minerals, the operator must be guided by his judgment in its use.

261. Machine for Making Mineral Sections.—A convenient apparatus for this purpose has been described by Williams^[167] and is represented in Fig. 57. It is supported on a substantial table provided underneath with electric batteries and a motor for driving the cutting disks seen on the top. The table is three feet six inches square and two feet nine inches high.

The grinding apparatus consists of two circular disks of solid copper, nine inches in diameter, and three-eighths inch thick, which may be used alternately as different grades of emery are required. They are attached either by a screw or square socket to a vertical iron spindle which revolves smoothly in a conical bearing. The grinding disk is surrounded when in use by a large cylindrical pan of tin, which is not shown in the cut, which has an opening in its center to allow of the passage of the spindle.

The sawing apparatus consists of a horizontal countershaft placed on a different part of the table and connected with the motor by a separate belt. It carries at one end a vertical wheel of solid emery, and at the other an attachment, level-table and guide for the diamond-saw. A small water-can with spout, not shown in the cut, is suspended over the edge of the table to keep the saw wet when it is in use.

The machine is very conveniently driven by a storage battery when street circuits cannot be drawn on.

For the details of making mineral sections, the works on petrography may be consulted.

262. Separation of Silt Particles by Specific Gravity Solutions.—In silt separates the specific gravity of the different mineral particles present may vary from graphite (1.9–2.3) to hematite (5.2–5–3).

The following list gives the specific gravities of some of the more common minerals which may be met with in soils:

The finest particles of silt are separated by gravity with great difficulty, inasmuch as they tend to remain suspended in the solutions for an indefinite period. With the coarser silts, however, useful data are often obtained by this method. The separation is preceded by extraction of the particles with hydrochloric acid to remove encrusted soluble matter, and by ignition to destroy any traces of organic matter. Those mineral matters which are soluble in acid or are changed by ignition must, of course, be sought for in separate portions of the silt,

263. Thoulet’s Solution.^[168]—The standard solution is of such a density that particles of 2.65 specific gravity-will just float thereon, using for this purpose a solution of about 2.7 specific gravity. The solution from which the above standard is prepared is made as follows:

One part of potassium iodid is weighed and placed in a beaker and one and one-quarter part of mercuric iodid is placed on top of it. Then water is added in the proportion of ten cubic centimeters to 100 grams of the mixture, and after some time (twelve to twenty-four hours), with occasional stirring, the salts will nearly completely dissolve. Filter from the undissolved residue and evaporate in a porcelain dish until crystals form on the surface of the liquid. Allow to cool, pour off the liquid from the crystals and evaporate the liquid for another crop. The first solution, after cooling, has a specific gravity between 3.10 and 3.20, the second a specific gravity of 3.28, practically the limit of density of the solution. The solution of 2.7 specific gravity and other densities are made by cautiously adding a few drops of water at a time and ascertaining the specific gravity by the Westphal balance or other convenient method.

The strong solution, according to Goldschmidt,^[169] may be prepared directly by using potassium iodid and mercuric iodid in the ratio of 1 : 1.24. Twenty-five cubic centimeters of water, 210 grams of potassium iodid, and 280 grams of mercuric iodid afford a solution of 3.196 specific gravity at 15°, on which fluorspar fragments will float.

264. Klein’s Separating Liquid.—A solution of cadmium borotungstate, of the composition 2H₂O,2CdO,B₂O₃,9WO₃ + 16H₂O, has been proposed by Klein^[170] for separating silt particles. This salt is obtained by dissolving pure sodium tungstate in five times its weight of water, adding one and a half parts of boric acid and boiling until, complete solution takes place. On cooling; the borax is separated in crystalline form. The mother-liquor after the removal of the crystals is carefully concentrated by boiling. By stirring the cold solution, there is a further separation of sodium borate and polyborate. This operation is continued until glass will float on the mother-liquor. The salt in solution then has the following composition: 4Na₂O,12WO₃,B₂O₃. To this boiling concentrated solution, is added a boiling saturated solution of barium chlorid, in the proportion of one part of the chlorid to three parts of the original double tungstate. An abundant pulverulent precipitate is formed, making the whole mass mushy. The mass is filtered under pressure and well-washed with hot water. The residue is then suspended in hot water containing one part in ten of hydrochloric acid of 1.18 specific gravity. It is then evaporated to dryness in the presence of an excess of hydrochloric acid and decomposed, by which process hydrated tungstic acid is separated. The boiling mass is taken up with water and the boiling continued for two hours with occasional addition of water to take the place of that evaporated, and the tungstic acid separated by filtration.

From the solution, beautiful quadratic crystals separate having the composition 9WO₃,B₂O₃,2BaO₂H₂ + 18H₂O. These are purified by several recrystallizations and freed from any scales of boric acid by washing with alcohol. Any reducing action, revealed by a violet coloration of the crystals, can be avoided by adding a few drops of nitric acid. From a boiling solution of these crystals, the cadmium salt desired is obtained by treatment with the proper amount of cadmium sulfate solution to precipitate the barium. The barium sulfate is separated by filtration. The cadmium borotungstate is soluble in less than ten parts by weight of water. From this solution it is obtained in pure form by evaporation under a vacuum, or by carefully concentrating on a water-bath and cooling. A saturated solution of these crystals at 15° has a bright yellow color and a specific gravity of 3.28.

If a dilute solution of the above salt be carefully evaporated on a water-bath, any violet color which may be present disappears when the specific gravity reaches 2.7. If the evaporation be continued until a crystal of augite will float on the hot liquid, crystals may be obtained on cooling which, dissolved in as little water as possible, make a solution which will almost support olivine. If the two solutions be united, the specific gravity of the mixture is 3.30–3.36. The highest attainable specific gravity; viz., 3.6, is produced by continuing the evaporation on a water-bath until the liquid will support olivine, and then allowing to stand in a closed place for twenty-four hours. The crystals of cadmium borotungstate thus obtained are freed as much as possible from the mother-liquor by drainage and then melted at about 75° in their own water of crystallization. A liquid is thus obtained on which spinel will float. The same concentration may also be obtained by careful heating on a water-bath. At its highest specific gravity this solution has an oily consistence and this renders its practical use in the separation of fine particles somewhat restricted. By filtering the liquor when a crystalline crust begins to form during evaporation, a cold solution of 3.360–3.365 specific gravity is obtained which is found practically useful. It has a higher specific gravity than Thoulet’s mixture, is not injurious to any of the mineral particles, not even of iron with which it is brought into contact, but the trouble of preparing it is far greater than that of the mixture of mercuric and potassium iodids.

265. Rohrbach’s Solution.—The solution of barium mercuric iodid recommended by Rohrbach^[171] for this purpose was originally prepared by Suchsin. The solution must be rapidly prepared on account of the tendency of the barium salt to decomposition. The solution is prepared by weighing rapidly 100 grams of barium and 130 grams of mercuric iodid, mixing the two salts well in a dry flask and adding twenty cubic centimeters of water. The mixture is raised to a temperature of 150°–200° on an oil-bath. The formation and solution of the double salt are promoted by constant stirring.

After solution, the liquor is boiled for a few minutes and then evaporated on a water-bath until it will bear a crystal of epidote. On cooling, a small quantity of a yellow double salt is separated by crystallization and the resulting mother-liquor is dense enough to carry a fragment of topaz. Inasmuch as the liquor is filtered with difficulty, the clear mother-liquor should be separated by decantation after standing for several days. This solution has the disadvantage of not being dilutable with water, the addition of which causes a separation of red mercuric iodid. Were this solution not so easily decomposed, it would prove of high value in silt separation.

266. Braun’s Separating Liquid.—In many respects the separatory solution proposed by Braun^[172] is superior to those already mentioned. It is the commercial methylene iodid, CH₂I₂, which has at 16° a specific gravity of 3.32, at 5° of 3.35, and at 25° of 3.31. It is a strongly refractive liquid having a refractive index of 1.7466 for the yellow ray.

As a separating medium the liquid is open to two objections; viz., first, it cannot be diluted with water and, second, it turns brown on heating or on long exposure to the sunlight.

When dilution is necessary, it should be accomplished with benzene or xylene. To bring the diluted liquor again to its maximum density, the benzene must be removed by evaporation, which causes a considerable loss in the liquid. When this substance becomes opaque, the transparency may be restored by removing the separated iodin by shaking with potash lye, washing with pure water, drying by the addition of pieces of calcium chlorid and filtering. The same result may also be reached by freezing and separating the liquid portion. The frozen portion on melting will have the density of the original liquid.

267. Method of Bréon.—Instead of a solution of a salt, Bréon^[173] has proposed to use salts in a fused state for separating mineral particles. Lead and zinc chlorids may be used for this purpose in a melted state, having the specific gravities of 5.0 and 2.4, respectively. By mixing the molten salts in different proportions, any desired specific gravity between the extremes mentioned may be secured. The fusion is accomplished at 400° in a test-tube. The silt is added gradually with constant stirring until a sharp separation is secured between the sinking and floating particles. After cooling, the tube is broken, the two parts separated, and the silt recovered by dissolving the mixed salts in hot water containing a little nitric acid. Only the coarser silts can be separated by this method. Fused silver nitrate, melting point 198°, specific gravity 4.1, has also been used for separation.

268. The Separation.—Forty cubic centimeters of the solution in the Thoulet process are placed in the separatory tube A, Fig. 58, together with from one to two grams of the silt and the stopper F inserted. The tube G is connected with a vacuum apparatus by means of which any air particles adhering to the mineral fragments are removed. The silt which sinks in the solution is removed after G has been disconnected by opening the cock C and sucking through B at I. The cock C is closed and the separated particles washed into a beaker at H after opening D. Water is next added to the materials left in A in quantities previously determined to secure a given specific gravity and thus a second, a third, etc., separation secured. An intimate mixture of the solutions in A can be effected by closing D, opening C, and blowing through B in such a way that no liquid is allowed to pass through C.

The quantity of water to be added in each case to secure a given specific gravity is determined by the formula v₁ = v(D − d)
d − 1, in which v is the volume of the solution, D its specific gravity, and d and v₁ the specific gravity desired and volume of the water to be added.

Example.—Let the specific gravity of the original solution be 3.2, its volume thirty cubic centimeters, and the desired specific gravity of the new solution 2.85.

Then v₁ = 30(3.2 − 2.85)
2.85 − 1 = 5.68.

The desired specific gravity is therefore secured by adding 5.68 cubic centimeters of water, which is easily accomplished by means of the graduations on the tube.

According to Rosenbusch,^[174] the calculated specific gravity as made above is not wholly reliable on account of the contraction which takes place. An empirical process is rather to be commended which consists in introducing a fragment of mineral of known or desired specific gravity and then adding water drop by drop until the fragment remains suspended in the mixture. Should too much water be added, the necessary increase in density can be secured by adding a little of the strong solution.

269. Method of Packard.—A separatory funnel, according to Packard,^[175] may be safely used to hold the solution while separation is going on. As the lighter minerals form the bulk of soils, the heavier constituting only a small percentage, it is well to use a wide funnel holding as much as one-half liter for quantitative separations, because a large quantity of soil, say 100 grams, is necessary from which to recover the small quantity of heavy particles satisfactorily. The soil is introduced into the solution contained in the funnel, agitated, stirred with a glass rod, and allowed to stand some time. This operation may be repeated as often as desired. Separation is not absolute by this operation, the heavy and light particles being sometimes so united that they sink or float together according as one or the other preponderates. There are also particles having so nearly the same specific gravity as the solution that they remain indifferent to its action in any position. After separation has been effected, the heavy portion is drawn off through the stop-cock of the funnel and the lighter is skimmed off the top. Both must be thoroughly washed from the adhering heavy solution for further examination with the microscope, and by chemical, microchemical, and blow-pipe tests. One who has familiarized himself with the appearance of minerals in minute fragments under the microscope, in ordinary and polarized light, will be able to determine some minerals in that way. But for certain identification it is necessary to ascertain their optical properties as is done in the case of the minerals in thin sections of rocks.

Illustration.—The following example from the work of Packard will serve to illustrate the results of separating a soil by the specific gravity method:

One hundred grams of soil, residual clay from the Trenton limestone, were placed in the Thoulet’s solution contained in the large separatory funnel. The heavy portion, after washing and drying, weighed 0.6886 gram, or 0.69 per cent. Of this, the magnet removed 0.1635 gram, or 0.16 per cent. This heavy material consisted of rounded yellowish and brown grains up to twenty-five millimeters in diameter, mingled with lustrous angular black grains which were seen under the microscope to be cubes with striated faces, cubes penetrating each other and aggregations of cubes. Combinations of cubes with octahedra and instances of the pentagonal dodecahedron were also observed. These forms, characteristic of pyrites, were also seen in the fine sand obtained as a residue on elutriating the same soil. As these crystals dissolved in hydrochloric acid, giving a strong iron solution, they were regarded as pseudomorphs of iron oxid after pyrites. The yellowish grains on treatment with acid left a grayish residue which contained some grains of quartz but was not wholly quartz. The lighter portion of the soil, over ninety-nine per cent, which floated in the Thoulet’s solution of 2.8 was next examined. It was colored red by the iron oxid which coated and adhered to the other minerals. It contained all the quartz, the feldspars if present, and the other minerals whose specific gravity is less than 2.8. It was examined by the microscope and found to consist largely of irregular grains of a mineral which acted on polarized light, obscured somewhat by the iron oxid, and was apparently quartz; and another mineral which was yellowish-brown in color and seemed to be dull and not transparent. Besides there was a large quantity of indistinguishable amorphous material. To clean these minerals the material was treated with hydrochloric acid to remove the iron oxid and other matter soluble in acid, when the quartz grains appeared transparent and gave interference colors in polarized light. But mingled with these were grains of the other mineral which now appeared grayish, dull, and without action on polarized light. The character of this mineral substance could only be determined by chemical analysis.

270. Harada’s Apparatus.—Although it has been affirmed by some analysts that in the subsidence of small particles it is advisable that the containing vessels have parallel sides, yet in the method just given, and in those about to be described, good results are obtained in a funnel or pear-shaped holder.

In the apparatus of Harada,^[176] Fig. 59, the separating vessel a is made of thick glass furnished with a glass stopper above and a glass stop-cock h below. The separating liquid and silt are placed in the pear-shaped vessel a, the stopper inserted, and the whole well-shaken. As soon as a ring of clear liquid is seen between the sinking and floating silt, the lower end of the apparatus is brought near the bottom of a conical glass b, the cock h opened and the heavy silt allowed to fall out. Very little of the liquor will flow out because of the air pressure. Should an air bubble enter the apparatus and be held at the stop-cock, it should be made to ascend by gently tapping. When all the heavy silt has passed into the conical glass, the cock h is closed and some water poured over the solution and silt in b. The separatory apparatus is now raised until the beveled end of it is in the water layer, when the water at once rises to h and thus washes all the silt particles adhering to the glass into b. The liquid in a may then be diluted by inverting the apparatus, adding the required amount of water through h, again shaken after closing h, and another separation secured as before.

This apparatus is somewhat easier to manipulate than Thoulet’s but does not admit of the same quantitative dilution of the separating liquid.

271. Apparatus of Brögger.—All silt separations in narrow tubes are open to the objection of permitting more or less flocculation. Some of the lighter particles are thus carried down by the heavier, and, on the other hand, some of the heavier float with the lighter. This disturbing action Brögger^[177] seeks to avoid by the following device, Fig. 60, a, b, c. The length of the apparatus is forty-six centimeters, and its greatest diameter 3.5 centimeters. The opening in the large stop-cock A is the same diameter as that of the apparatus at that point. The cubical content of the apparatus with A open and B closed is about seventy-five cubic centimeters. In conducting the separation the cock B is closed, the separating liquid and silt introduced, A being open, the stopper K inserted and the whole well-shaken. In the first separation, the silt S, lying over B is contaminated with some of the lighter particles S′₂, while the lighter particles above A, S₂, are mixed with some of the heavier particles, S′₁. After closing A the apparatus is again well-shaken and inverted as in Fig. 60 b. The two parts of the silt will now undergo another separation as indicated. The apparatus is now carefully inclined as in c, when the various grades of silt will flow in the directions indicated by the arrows, but without mixing, passing each other on opposite sides of the apparatus. When the movement is complete, A is carefully opened, the apparatus still being held as in c, and the light silt formerly between A and B will flow above A, while the heavy silt above A will flow down and join the silt collected over B. This operation may be repeated until a perfect separation is effected. Finally B is opened and the heavy silt collected in a beaker, and the lighter silt then removed from the upper part of the apparatus.

272. Method of Wülfing.—A somewhat more convenient method of purifying the silt segregates and freeing them of mechanically occluded particles of differing specific gravities has been proposed by Wülfing.^[178] An elliptical ring of heavy glass tubing carries glass stop-cocks A and B, Fig. 61, at the two extremities of the ellipse, each arm of which is provided with a lateral glass-stoppered neck. The perforation in the stop-cocks has the same diameter as the sides of the ellipse. The apparatus has an interior cubical content of about forty cubic centimeters. Thirty cubic centimeters of the separating fluid are introduced through one of the lateral apertures and brought to the same height in the two arms by opening the cock B. The silt is then introduced in equal quantities into each of the arms. The stoppers having been inserted, the whole is well-shaken. At the beginning of the separation, the apparatus being held in position 1, the lighter soil above and the heavier soil below are somewhat mixed by reason of flocculation and mechanical entanglement. At this point B is opened and the apparatus placed in the inclined position 2. The heavier particles S + l, on the right arm, are thus united with the same class of particles in the left arm making 2S + 2l. This operation is hastened by opening A and allowing the higher column of liquid in the right arm to pass into the left. The liquid in the left arm is allowed to rise to A. After all of S + l in the right arm has passed into the left B is closed, the apparatus then placed back in position 1 and inclined in the opposite direction until L + s in the top of the left arm has been transferred to the L + s in the top of the right, and the same quantity of liquid is found in each arm. The operation is then repeated and this continued until all S + s is found in the bottom of the left arm and all L + l in the top of the right arm.

273. Separation with a Magnet.—Particles of magnetic iron oxid are easily separated from the fine soil particles by means of a magnet. A strong bar or horseshoe magnet may be used. Electro-magnets are rarely necessary except for the separation of particles of feeble magnetic power. Particles of iron which may be found would owe their origin to the mortars in which the soil had been pulverized, or they might come from a recently crushed meteorite. Some minerals, as limonite, after ignition are attracted by the magnet and it is advisable to subject a part of the sample to this treatment. The best method of separation consists in spreading the particles evenly on paper and gradually bringing the magnetic particles to one side by moving the magnet underneath.

274. Color and Transparency.—But little can be learned from the color and transparency of the smallest silt particles, but these properties in the larger grains have considerable diagnostic value. Many minerals of distinct color appear wholly colorless in petrographic sections or in silt particles, as for instance, highly-colored quartz. On the other hand, even the smallest particle of chlorite will show its distinctive tint. The colors in some minerals are due to occluded matter not essential to their structure, and these foreign bodies would naturally escape when the crystal mass is reduced to an almost impalpable powder.

275. Value of Silt Analyses.—As in the case of chemical analyses a silt analysis of a soil which is not typical or representative has little value. On the other hand, a systematic separation of soils into classes of particles can not fail to reveal a definite correspondence of mechanical composition to soil properties. The production of a crop is the result of certain functions, chief among which are temperature, moisture, and plant food. In a given soil the temperature is markedly affected by its physical state. It has been demonstrated in previous paragraphs that the circulation of moisture in the soil and its capacity to be held therein are chiefly functions of the state of aggregation of the soil itself. The availability of plant food in a soil is not measured by its quantity alone, but rather by its state of subdivision. It is not therefore a matter of surprise that the fertility of a soil is found, caetèris paribus, to be commensurate to a certain limit with the percentage of fine silt and clay which it contains. It is true that two soils quite different in fertility, may have approximately the same silt percentages, but in such a case it is demonstrable that even in the poorer soil the measure of fertility is largely the percentage of fine particles and not its actual content of plant food. In other words, almost all soils, even the poorest, have still large quantities of plant food, but these stores, owing to certain physical conditions, are not accessible to the rootlets of plants. An illustration of this is seen in the use of concentrated fertilizers. It might seem absurd to suppose that the addition of 100 pounds of sodium nitrate would prove useful to a plat containing already many tons of nitrogen; but the nitrate is at once available and its beneficial influences are easily seen.

The full value of silt analysis will only be appreciated when many typical soils from widely separated areas are carefully studied in respect of their chemical and physical constitution and the character of the crops which they produce.

AUTHORITIES CITED IN PART FOURTH.