Jleto gorfe »tate College of Agriculture &t Cornell Umbenrttp Stfjaca, JH. g. Hibrarp P. SCHWEITZER. [From the Catalogue of the University of the State of Missouri.] QD^f CONTRIBUTIONS S */"/ FROAt THE ABORATORY OE THE STATE UNIVERSITY. 3N THE TRUE COMPOSITION OF COAL, AND ON THE METHODS OF ARRIVING AT IT; WITH DEDUCTIONS* AND REMAKES ON COAL IN GENERAL; ILLUSTRATED ON A SAMPLE OF COAL FROM THE LOWER COAL SERIES OF MISSOURI. THE WATER-SUPPLY OF COLUMBIA, BOONE COUNTY, MISSOURI; BEING AN EXPOSITION OF THE ORIGIN OF THE SPRINGS AND SUBTERRANEAN WATER-COURSES OF THE TOWN AND NEIGH- BORHOOD, WITH SOME ANALYSES OF CISTERN WATER. P. SCHWEITZER, Ph. D. Professor of Analytical and Applied Chemistry. JEFFERSON CITY: ItEGAN 4 CASTER, STATE FKINTEKS AND BINDERS. X 1875. Cornell University Library The original of this book is in the Cornell University Library. There are no known copyright restrictions in the United States on the use of the text. http://www.archive.org/details/cu31924002988495 [From the Catalogue of the University of the State of Missouri."] CONTRIBUTIONS FROM THE LABORATORY OF THE STATE UNIVERSITY. A. ON THE TBUE COMPOSITION OP COAL, AND ON THE METHODS OP ARRIVING AT IT ; WITH DEDUCTIONS AND REMARKS ON COAL IN GENERAL ; ILLUSTRATED ON A SAMPLE OP COAL PROM THE LOWER COAL SERIES OP MISSOURI. B. THE WATER-SUPPLY OP COLUMBIA, BOONE COUNTY, MISSOURI; BEING AN EXPOSITION OP THE ORIGIN OP THE SPRINGS AND SUBTERRANEAN WATER-COURSES OP THE TOWN AND NEIGH- BORHOOD, WITH SOME ANALYSES OP CISTERN WATER. P. SCHWEITZER, Ph. D. Professor of Analytical and Applied Chemistry. JEPPERSON CITY: BEGAN 4 CAETEIt, 8TATE PRINTERS AND BINDERS. 1875. APPENDIX. [A.] CONTRIBUTIONS FROM THE LABORATORY OF THE STATE UNIVERSITY. By P. SCHWEITZER, Ph. D., Professor of Analytical and Applied Chemist/-]/. ON THE TRUE COMPOSITION OF COAL, AND ON THE METHODS OF ARRIVING AT IT; WITH DEDUCTIONS AND REMARKS ON COAL IN GENERAL; ILLUSTRATED ON A SAMPLE OF COAL FROM THE LOWER COAL SERIES OF MISSOURI. A. THE COAL. The following investigations were originally undertaken for the purpose of determining the origin of the mineral matter of the spring- waters, issuing from the ground in various parts of Boone county, and extended afterwards, so as to serve as a first contribution to our know- ledge of the Coals of Missouri, and if time and health permits, of the Coals of the three great western Coal Fields. Though at the begin- ning only of this work, I feel satisfied, that from a number of investi- gations, similar to the one I present here of Boone county Coal, clearer views regarding the origin, relative age, and manner of forma- tion of Coal can be obtained, than from isolated phenomena or experi- ments of necessarily short duration. It is true, inductions should only 156 UNIVERSITY OF THE STATE OF MISSOURI. be drawn from a number of facts, and I would for this reason enlist in the work of solving one of the great scientific questions of the day all chemists, who consider it sufficient reward, to work patiently and unselfishly for the advancement of human knowledge. A determina- tion of the true composition of Coals belonging to the same Coal- basin would be a first step in this direction. Neither elementary nor proximate analysis alone furnish the desired information ; but when taken together with additional deter- minations of the constituents of the Ash of Sulphur and of Sulphuric Acid, are quite sufficient for the accurate calculation of the true com- position of Coal. The Coal, which I selected for analysis, came from the mine of , a few miles from Columbia, and was remarkable for the large percentage of Sulphuret of Iron, which it contained. It was burned in the furnaces of the Scientific Building of the University during the winter of 1873 to '74, during which time I selected speci- mens of the Coal, as it was delivered at the Building, until I had about ten pounds of it, representing, I think, well the average quality* of the Coal of that particular seam, which is one of the three lowest ones in the Lower Coal Series of the State. The pieces selected remained in a closet during the summer, and were apparently not altered, when they were pulverized in the fall for examination. Some change, however, had probably taken place, though the oxidation of the Sulphuret is no doubt going on in the bed itself, resulting in the waters, percolating them, becoming charged with mineral salts, and appearing often in the form of mineral springs at a greater or lesser distance from the Coal-bed. The pulverized Coal, while under examination, was kept in a cool room and in a well stoppered bottle, so as to prevent, if possible, any further oxidation. In stating the results of my analysis I shall not attempt to give all figures, but simply the amount of substance taken, the percentage obtained and the method followed. Gr. stands throughout for gramme. 1. Elementary Analysis. For the determination of Carbon and Hydrogen 0.5 gr. of Coal were taken each time ; the combustions were conducted in a char- coal-furnace with pure and perfectly dry Lead Chromate, with a spiral of Metallic Copper of about two inches in length placed in front. Four combustions were made, in the last of which the Carbon determination miscarried by the breaking of the absorption-apparatus. The Nitrogen was determined in 2 gr. and 2.5 gr. of Coal respect- UNIVERSITY OF THE STATE OP MISSOURI. 157 ively ; the Soda-Lime employed for this purpose was prepared by myself, and was entirely free from nitrogenous matter. The escaping Ammonia wa3 collected in dilute Hydrochloric acid, the Platinum salt prepared and the latter ignited. From the weight of Metallic Platinum the amount of Nitrogen was calculated. The following per- centages were obtained : Carbon 50.76 p. c. 50.56 p. c. 50.90 p. c. Hydrogen = 152.22 p. c. Mean = 50.7400 p. c. 4.5422 p. c. 4.5089 p. c. 44600 p. o. 4.5222 p. c. 18.0333 Mean = 4.5083 p. c. Nitrogen = 0.9000 p. c. 0.8720 p. c. 1.7720 Mean == 0. p. c. S. Proximate Analysis. Water and volatile matter were determined in 2 gr. of coal; the former by heating 15 minutes at a temperature of 112° C. and weigh- ing then from 5 to 5 minutes, until the weight commenced to increase ; and the latter by heating the platinum crucible over a Berzelius-Lamp, with a chimney placed over it ; no blast was employed, and the tem- perature to the end a bright cherry-red. The Carbon could not be burned off in this way (Methylic-Alcohol was the source of heat) and the ash had to be determined in separate samples. A large quantity of ash was desirable, and 10 gr. of Coal were taken for this purpose, placed in an open Platinum-Capsule, and the latter heated in the muffle of a muffle furnace, until the weight remained constant. The percentages were as follows : Water = 5.844 p. c. 5.025 p. c. 5.451 p. c. 16,420 Volatile matter 28.194 p. c. 28.457 p. c. 28.554 p. c 85.205 Mean = 5.4733 p. c. Mean = 28.4017 p. c. 158 UNIVERSITY OP THE STATE OF MISSOURI. Ash = 17.803 p. c. 17.729 p. c. 17.332 p. c. 52.864 Mean = 17.6213 p. c. The color of the ash was pink, with numerous white specks in it ; these latter, I think, were derived from the destruction of the organic matter of the Coal, and were originally part of the plants that formed it; they were mixed with the finely-pulverized brown oxide of the roasted Sulphuret, and with larger grains of a yellowish color, which I am inclined to consider Clay. No remains of microscopic animal life were detected by me in the ash. Upon placing 10 gr. of this Coal over pure, distilled Sulphuric Acid, it lost the fol- lowing percentages of water — each subsequent-mentioned percentage including all pre- vious ones : In 4 days, 1.923 p. c. In 9 days, 1.977 p. c. In 16 days, 1.985 p. c. In 24 days, 1.989 p. c. The same sample, placed now in a drying apparatus, through which a current of heated air of 60° F. was passed, lost — In 2 hours, 2.427 p. c. In 6 hours, 3.072 p. c. In 8 hours, 3.232 p. c. S. Determination of Sulphur. The total amount of Sulphur existing in the Coal was determined by deflagrating in a large Platinum crucible a mixture of 2 gr. of Coal with 12 gr. of Sodium Carbonate and 12 gr. of Potassium Nitrate. After freeing the Hydrochloric Acid solution, which was free from any undissolved particles, from Silica and Nitric Acid, the Sulphuric Acid was precipitated by Barium Chloride. The thoroughly washed precip- itate was dissolved in a large Platinum dish in concentrated Sulphuric acid, re-precipitated by water, filtered, washed and weighed. In ad- dition to this determination, the Sulphuric Acid, existing as such in the Coal, was estimated in 4 gr. of the Coal (a) by boiling with Hydro- chloric Acid, precipitating and proceeding as before, and (5) by boil- ing with Sodium Carbonate, acidulating with Hydrochloric acid and finishing in the same manner. Here are the results : Total Sulphur = 11.8563 p. c. 11.7530 p. c. 23.6083 Mean = 11.8046 p. c. UNIVERSITY Off THE STATE OF MISSOURI. 159 Sulphur existing as Sulphuric Acid : a = 2.4660 p. c. 6 = 2.4740 p. c. 4.9400 Mean = 2.4700 p. c. Equal to 6.1750 p. c. of Sulphuric Acid. The solution, obtained by Sodium Carbonate, evolved a small amount of Sulphuretted Hydrogen Gas upon the addition of acid; this was owing to the presence of Sulphuret of Sodium formed by the action of the Carbonate upon free Sulphur, which I had reason to sus- pect and afterwards proved to be present in the Coal. The decompo- sing Sulphuret of Iron is converted into Sulphate with separation of Sulphur, and the latter can readily be extracted by Carbon Disulphide, and obtained by evaporating the solution ; a fact which explains, with- out constraint, the excess of Sulphur over the Iron, which is found to exist in nearly all of the Western Coals. T. G. Wormley* and Rush Emeryf furnish a number of analyses illustrative of this point; their Coals were altered and contained Sulphuric Acid, and this, I think, will be found to be the case with all Coals in which such excess of Sulphur is detected, unless, indeed, it has been washed away by per- colating waters. Future investigations may throw more light upon this point, and enable us to calculate, perhaps, the amount of oxidation to which a Coal has been subjected; for if it be found true, as I suspect it will be, that decomposing Pyrite, under the conditions under which we find it in Coal, yields by oxidation a definite amount of Sulphur, this latter would, of course, be a measure of the oxidation that has taken place, and a measure at the same time of the quantity of Sulphuric Acid which must.have been formed, and been either retained by the" mineral constituents of the Coal or washed away by telluric waters. The excess of Iron over the Sulphur, which Rush Emery reports in two cases, may be easily explained by the presence within the Coal of insoluble Iron compounds, such as Silicates, which, no doubt, exist in some and perhaps in all Coals containing much ash. The elementary composition of this Coal then would be : Carbon = 50.740 p. c. Hydrogen = 4.50S p. c. Oxygen = 14.440 p. c. Nitrogen = 0.886 p. c. Sulphur = 11.805 p. c. Ash = 17.621 p. c. 100.000 * Geological Survey of Ohio ; Beport of Progress in 1870. t Sill. Am. Jour., January, 1872. 160 UNIVERSITY OF THE STATE OP MISSOURI. In which the Oxygen would be the only doubtful figure, from the fact that Sulphur and ash together might not represent the mineral mat- ter in the Coal. The proximate composition would be : "Water = 5.473 p. c. Volatile matter = 28.402 p. c. Fixed Carbon = 48.504 p. c. Ash = 17.621 p. c. 100.000 In which every figure, except that of water, is uncertain ; the ash, as it does not represent the quantity of mineral matter in the Coal ; the Fixed Carbon, as it includes Sulphur, Oxygen, Hydrogen and Nitro- gen ; and the Volatile Matter in so far as it is meant to represent Bitumen or Volatile Hydrocarbons. Two further experiments were made for the purpose of ascertaining how two other methods, proposed for the determination of total Sulphur in Ooals, compared in accuracy with the one followed by me. In the one (a) a mixture of 2 gr. of Coal with 1 gr. of pure, precipitated Calcium Carbonate, was moistened with Ammonia, dried and ignited in a muffle furnace ; the ash, which was rather lighter in color than the pure ash, was boiled with Hydrochloric Acid, and Sulphuric Acid determined in the usual way. In the other (b) 2 gr. of Coal were treated for nearly a day with Hydro, chloric Acid and Bromine "Water ; this treatment was repeated after filtering off the solution, and Sulphuric Acid determined separately in each fluid. The results, ex- pressed in per cent, of Sulphur, are — u. = 5.8200 p. c. i = 7.3320 p. c. 0.8120 p. c. 8.1440 p. c. Both determinations show so marked a deficiency in the" amount of Sulphur found, that the methods, to say the least, prove impracticable. I will add that in the first experiment, all Carbonic Acid of the Lime had disappeared, there being no effer- vescence observed by the addition of acid, and that a portion of the Lime existed in the caustic state, though some of it had united with Silica to a Silicate, which was easily decomposed with separation of gelatinous Silicic Acid. I am aware that the method, as actually carried out, is somewhat different from mine but consider it, in any case, doubtful to be able to take sufficient Lime, even in the caustic state, to fulfill the three conditions requisite for obtaining accurate results, namely: to envelope completely all particles of Sulphuret of Iron ; to allow the air to have access to it, and to retain all Sulphurous Acid formed by air and heat. The other method, though answering perfectly well in the case of Copper Pyrites, must be rejected for Coal. 4. Analysis of Ash. The first of the three determinations of ash yielded 1.7803 gr. and served for the estimation and independent analysis of the portions, UNIVERSITY OF THE STATE OP MISSOURI. 161 which were soluble and insoluble in Hydrochloric Acid. The inso- luble portion was freed from Silica by Ammonium Fluoride and Sul- phuric Acid, and the bases determined in the resulting solution. I chose this process on the supposition that the whole of it consisted of Silica. The second determination yielded 1.7729 gr. of ash, which were fused with Sodium Carbonate, and analyzed in the usual way. The third determination left 1.7332 gr. of ash, which were exam- ined for alcalies with a perfectly negative result. In these Analyses Ferric oxide, Alumina and Phosphoric Acid were precipitated by Ammonia ; the weighed precipitate was dissolved in fusing Potassium Disulphate, and the Iron, after adding Tartaric Acid and Ammonia, precipitated by Ammonium Sulphide ; the washed precipitate was dissolved, oxidized, reprecipitated and weighed. Alu- mina and Phosphoric Acid were then obtained by subtraction. In the Analysis of ash number two, the filtrate containing these two sub- stances was evaporated with the addition of Sodium Carbonate and the dry mass fused with Potassium Nitrate. After dissolving the fused mass in water, Nitric Acid was added to acid reaction and Phosphoric Acid precipitated by Molbydic Acid solution. Sulphuric Acid was precipitated after the removal of Magnesia ; and as the Barium Sulphate might have contained some Oxalate, the washed precipitate was rinsed back into a beaker and heated with a little Bromine water before collecting it definitely for determination. I. 1.7S03 Gr. op Ash. 83.7275 p. c. portion soluble in acid. 16.2725 p. c. portion insoluble in aciii. 100.0000 Calculated for the mean percentage of Ash (17.6213). 83.724 p. c. = 14.753 p. c. (of Coal.) 16.27(3 p. c. = 2.863 p. c. (of Coal.) 100.000 17.621 A. Solution in Hydrochloric Acid : Ferric Oxide = 75.7853 p. c. Manganic Oxide = 1.1801 p. c. Alumina = 5.0609 p. c. Lime = 0.3673 p. c. Magnesia = 0.1313 p. c. Phosphoric Acid = 0.1404 p. c. Sulphuric Acid = 0.7635 p ; c. 83.4286 162 UNIVERSITY OF THE STATE OF MISSOURI. B. Insoluble residue : Ferric Oxide = 0.1476 p. c. = 0.0260 p. o. (of Coal.) Alumina = 2.1918 p. c. = 0.3862 p. c. (of Coal.) Magnesia = 0.3223 p. c. = 0.0568 p. c. (of Coal.) 2.6617 II. 1.7729 Ge. of Ash. Silica = 14.343S p. c. Ferric Oxide = 75.8596 p. c. Manganic Oxide = 0.8001 p. c. Alumina = 7.6630 p. c. Lime = 0.4287 p. c. Magnesia = 0.3224 p. c. Phosphoric Acid = 0.1404 p. c. Sulphuric Acid = 0.6618 p. c. 100.2198 HI. 1.7332 Gr. ov Ash. No Potassa and no Soda present. The mean composition of the ash, as obtained from analyses one and two, is-, therefore : Silica = 14.3438 p. c. = 2.5204 p. e. (of Coal.) Ferric Oxide = 75.8962 p. c. = 13.5739 p. c. (of Coal.) Manganic Oxide = 0.9901 p. c. = 0.1745 p. c. (of Coal.) Alumina = 7.4578 p. c. = 1.3141 p. c. (of Coal.) Lime = 0.3980 p. c. = 0.0701 p. c. (of Coal.) Magnesia = 0.3881 p. c. = 0.0684 p. c. (of Coal.) Phosphoric Acid = 0.1404 p. c. = 0.0248 p. c. (of Coal.) Sulphuric Acid = 0.7126 p. c. = 0.1256 p. c. (of Coal.) 100.3270 17.8718 The ash is remarkable for the total absence of Alcalies and Chlo- rine, for the small amount of Phosphoric Acid, and for the compara- tively large amount of Manganese which it contains. The insoluble Kesidue, consisting of Silica, Alumina, some Magnesia and a little Iron existed, I think, as such in the Coal, perhaps in the form of an insoluble Silicate, f. e. clay, and was precipitated from the muddy waters of the Lagoons at the same time with the vegetable matter, which produced the Coal. Nearly the whole of the Alumina, inso- luble and soluble, of this and other Coals is derived from such a source. It is itself no constituent of the ash of recent plants and no more likely to have been one of the ash of plants of the Carboniferous period. In factits very properties and its constitution seem to be unfa- vorable to its passing through membranes or capillary openings. That portion of Alumina, which is soluble in Acid, becomes thereby sugges- UNIVERSITY OF THE STATE OF MISSOURI. 163 tive of the decomposition of a part of the Silicate by means of Sul- phuric Acid, appearing in numerous springs of aluminous and vitriolic waters, which may form beds of Gypsum and Ochre during their course, and is attributable to the reverse of the process, which during submerg- ence produced the Sulphuret of Iron in the Coals by the action of decaying vegetable matter upon Salts of Iron. 5. Analysis of the aqueous Solution of Coal. 201. 1 gr of Coal were packed into a tall Glass-Funnel with Glass- stopcock, and washed with small portions of water (about 100 cc at a time), which were allowed to remain in contact with the Coal for 21 hours. By opening the stopcock, the fluid was run every morning into a large bottle, and fresh water poured upon the funnel. When 2140 cc had been collected, every trace of soluble matter was deemed to have been removed, and the solution, the first portions of which were yellow, while the rest was colorless, was subjected to Analysis. A large number of determinations were made, originally for a differ- ent purpose, as before stated, and which I shall have occasion to de- scribe more particularly in another paper. I will mention here only the composition, as obtained by Analysis of 1018.5 cc of the liquid, representing 100 gr. of Coal, and expressing therefore direct weight in gr. as well as percentages. Silica, Iron, Alumina, Lime and Magnesia were determined in one portion ; Sulphuric Acid in another; Ferrous Oxide in a third; and in a fourth, fifth and sixth search was made for Alcalies, Chlorine and Phosphoric Acid, with perfectly negative result, no trace of either of them proving to be present. The following is the composition of the liquid : Silica = 0.0076 p. c. Ferric Oxide = 0.9S92 p. c. Alumina = 0.1509 p. c. Ferrous Oxide = 3.0479 p. c. Lime = 3403 p. c. Magnesia = 0.0150 p. c. Sulphuric Acid = 5.8075 p. c. 10.3584 Upon evaporating and igniting this solution, there would plainly be volatilized all Sulphuric Acid, except 0.5163 p. c. united with Lime and Magnesia, while the Ferrous Oxide would take up Oxygen and become converted into Ferric Oxide. The quantity of ash therefore, which would be left by this operation, could be found by subtracting; 164 UNIVERSITY OP THE STATE OP MISSOURI. -from the total weight of the residue all Sulphuric Acid minus 5163 -gr. and 0.3387 gr. of O, requisite for the oxidation of FeO., this would leave 5.4059 p. c. of ash. One of the results of the examination becomes apparent, namely, that the ash does not express the quantity of mineral matter in Coal, and that therefore by assuming this to be the case, grave errors may be committed in the calculation of the Oxygen of the Organic Matter, a knowledge of which I hold to be essential in tracing the change, which Cellulose has undergone in becoming Coal. Oxygen is reduced from 44.6 p. c. in Cellulose to about 3 p. c. in Anthracite ; Hydrogen from 6.3 p. c. to about 2 p. c. The range in the former case is through 41.6 degrees, that in the latter through 4.3 de- grees. We can easily understand, that a method, which arranges •Coals with all their various shades of Composition within a compass of 41.6 degrees must be freer from error than one in which the compass is only 4.3 degrees. If the amount of Oxygen in the Organic Matter of Coal could be determined accurately and directly, we would have no need of the somewhat round-about way, followed by me ; but until such method is discovered, indirect means must be employed to reach this important result. It is true, though, that in Coals, which are free from Sulphur and Iron, the ash is a measure of the mineral matter in them, but when Iron is contained in the ash, even in the absence of Sulphur, this becomes already doubtful ; and I think that only in cases, where it can be proved to exist in some unsoluble form (unso- luble in Acid) the ash may be supposed to represent the amount of Mineral Matter in the Coal; whenever the Iron is in the soluble form, ■the degree of oxidation, in which it exists in Coal, should be ascer- tained and correction be made for it by adding the difference between f the two states of oxidization to the Oxygen. Without such correction the error will increase with the amount of Sulphuret and the degree •of weathering, without however becoming so small, that it could in safety be overlooked. 6. Composition of the Mineral Matter in this Coal. The portion soluble in Hydrochloric Acid is obtained by subtrac- ting from the constituents of the ash all that is soluble in water and insoluble in Acid, and also the remainder of that part of Iron, Man- ganese and Sulphur, which is given as Sulphuret. In calculating the amount of Sulphuret present 6.5420 p. c. of Iron and Manganese would require 7.4791 p. c. of Sulphur to form Disul- phuret, while 9.3376 p. c. are available. This excess of 1.8555 p. c. of Sulphur is contained in the Coal in the free state, and not in combi- UNIVERSITY OF THE STATE OS 1 MISSOURI. 165 nation with the Iron in a higher state of Sulphurization, as Kush Emory (*) supposes, nor also united with Organic Matter, as suggested by E. B. Andrews (f). I base my reasons for declining to accept their views upon the existence of free Sulphur in the Coal, and upon an Analysis (see Litt. D.) of a solution, obtained by boiling a portion of the washed Coal (obtained under No. 5) in Hydrochloric Acid. Silica = 0.0076 p. c. Ferric Oxide = 0.9892 p. c. Alumina = 0.1509 p. c. Ferrous Oxide = 3.0479 p. c. Lime = 0.3403 p. c. Magnesia = 0.0150 p. c. Sulphuric Acid = 5.8075 p. c. 10.3584 Soluble in water, Alumina = 0.7770 p. c. Lime = 0.0577 p. c. Phosphoric Acid = 0.0248 p. c. Sulphuric Acid = 0.3675 p. c. 1.2270 Soluble in acid. Silica = 2.5204 p. c. Ferric Oxide = 0.0260 p. c. Alumina = 0.3862 p. c. Magnesia = 0.0568 p. c. 2 9S94 Iron Disulphuret = 13.7582 p. c. Manganese " = 0.2629 p. c. Sulphur = 1.8555 p. c. Insoluble in acid (Clay. 15.8766 Sulphuret and Sulphur. Or, to condense it: 5.4104 p. c. soluble portion (except Sulphuric Acid). 2.9894 p. c. insoluble portion (Silicate). 14.0211 p. c. Sulphuret. 6.1750 p. c. Sulphuric Acid. 1.8555 p. c. Sulphur. 30.4514. By subtracting from the above amount all Sulphuric Acid, less the quantity actually found in ash, and also all the Sulphur, and ad- ding to the product sufficient Oxygen to oxidize Iron and Manganese, * Sill. Amer. Journal, January, 1872. t Geological Survey of Ohio, 1870, pp. 224, 412. 166 UNIVERSITY OF THE STATE OP MISSOURI. we obtain 18.2106 p. c, which agrees closely enough with the per- centage of ash found, to prove the correctness of the calculation. T. "G. Wormley in his excellent report (*) mentions a Coal (of New Straitsville, 3d seam), having an excess of Sulphur over the Iron, which if I understand him correctly, he suggests to be in combination with organic matter ; his suggestion would seem to be strengthened by the fact that Coke, obtained from the same Coal, still retained 0.26 p. •c. of Sulphur, while 0.027 p. c. were only found in the ash, which added to 0.088 p. c. united with all the Iron present as Disulphuret, would still leave an excess of 0.147 p. c. of Sulphur unaccounted for, which were to exist then in Coke in combination with organic matter. I think the fact of such a combination would be difficult to realize, as no organic substance free from ash, can be heated to redness without losing its Sul- phur, (f) The Coal contained no doubt Sulphuret, Sulphuric Acid and Sulphur, and I am inclined to ascribe the excess of Sulphur in the Coke, a little more than 0.147 p. c., to errors incidental to the analytical determination of Sulphuric Acid, especially as the weight of Barium Sulphate, which would correspond to 0.147 p. c. of Sulphur in 5 grains of substance analyzed, would amount to only 0.0035 gr. At the same place ten analyses of Coal ashes are given, in each of which Sulphur is reported present, be- sides Sulphuric Acid. Supposing the Reagents to have been pure, and the ash properly prepared, that Sulphur must have existed as Barium or Strontium Sulphate. 7. Composition of the Coal. The composition of the Coal, then, is represented as follows : Carbon = 50.7400 p. c. Hydrogen = 3.9001 p. c. Nitrogen = 0.8860 p. c. Oxygen = 8.5492 p. c. Water = 5.4733 p. c. Mineral matter = 30.5414 p. c. 100.0000 The organic matter in it by : Carbon = 79.19 p. c. Hydrogen = 6.09 p. c. Nitrogen = 1.38 p. c. Oxygen = 13.34 p. c. 100.00 Or, without the Nitrogen, by : Carbon = 80.30 p. c Hydrogen = 6.18 p c. Oxygen = 13.52 p. c. 100.00 (*) Geological Survey of Ohio, 1870, pages 412, 418, 428. t Gemlin-Handbook of Chemistry, Vol. XII., page 78-speaking of the efiect of heat on organic compounds, says : " If the compounds contain (01, Br, I or) Sulphur, these elements, if they do not separate in the free state, or enter into volatile organic compounds, are given off in combination with Hydrogen in the form of (HC1 HBr HI or) Hydrosulphuric Acid. Part of the Sulphur (and CI) may also be evolved in'the form of Sulphide of Carbon (or Chloride of Carbon). UNIVERSITY OP THE STATE OP MISSOURI. 167 In comparing the two amounts of Oxygen, obtained here and un- der No. 2, we find a much smaller difference than might have been anticipated; and though this difference is probably not a constant fig- ure, I suppose one-ninth might be subtracted from the Oxygen of all Coals containing Sulphur and Iron, in which Oxygen is determined in the ordinary way by subtraction, in order to arrive at a figure which would be a close approximation to truth, and offer a basis for compar- ison. The number of ultimate analyses ef western Coals is small, and I have at present no access to their records ; but those few that I have been able to compare, show within the same basin those Coals of a lower geological horizon to contain more Oxygen and Hydrogen, and less Carbon, than those placed above them, a difference, which is equally noticeable in the lower and upper portions of Coal of the same seam. Any marked exception to this rule will be owing to ge- ological disturbances of the beds, during and after the formation of the Coal, in consequence of which it may have become dry and exposed to the action of atmospheric Oxygen. B. THE COKE. The amount of Coke obtained from the Coal is 66.125 p. c. (See A 2). Its consistency and hardness is greater than might be anticipated, and only a small portion remains loose or in powder in the coking vessel. The Coal therefore belongs to the class of dry or sinter Coals with long flame, which when free from Pyrite are so excellent a fur- nace fuel. I trust that at no distant day means will be discovered by which our Coals can be freed from deleterious admixture, so that Mis- souri ores can be smelted by Missouri Coals. The analyses and indi- vidual determinations in Coke were made in the same manner, as thos 9 in Coal ; I refer therefore to them for the methods. 1. Elementary Analysis. Carbon = 58.140 p. c. 58.580 p. c. 116.720 Mean = 58.3600 p. c. Hydrogen = 1.4511 p. c. 1.5155 p. c. 2.9666 Mean = 1.4833 p. c. Nitrogen = 0.5333 p. c. (In 4 gr. of Coke. S. Determination of Sulphur. Sulphur = 13.1200 p. c. The coke contained no Sulphuric Acid, (boiling Hydrochloric Acid extracted none, but caused an evolution of Hydrosulphuric Acid, proving the presence of a lower Sul- 168 UNIVERSITY OF THE STATE OF MISSOURI. phuret,) which had partly been reduced and partly been volatilized, with the free Sul- phur and a portion of the Sulphur of the Pyrite. 13.12 p. c. of Sulphur in the Coke are equivalent to S.6756 p. c. of it in the Coal, demonstrating a loss of only 3.129 p. c. by coking. Calculating the Sulphates of Iron, Lime and Magnesia to become reduced to Mono-sulphurets, there would be volatilized— 1.8555 p. c. of free Sulphur. 0.4S04 p. c. Sulphur from rest of Sulphuric Acid. 0.7931 p. c. Sulphur from Pyrite. 3.1290 I confess that a loss of 0.7931 p. c. of Sulphur, or only one tenth of the Sulphur oi the Pyrite is rather smaller than might have been expected. 3. Composition of Coke. The mineral matter of the Coke consisted no doubt of the mineral matter in the Coal, less all Sulphuric Acid, all Sulphur and all Oxygen of the soluble bases, plus the Saiphur actually found, calculated in p. c. of the Coal. The product increased in the proportion of 66.125 : 100 would indicate percentages. 6.1750 p. c. of Sulphuric Acid (of Coal.) 9.3346 p. c. of Sulphur (of Coal.) 1.0773 p. c. of Oxygen (of Coal.) 10.5869 30.4514 p. c. of mineral matter (of Coal.) 16.5S69 p. c. volatilized. 13.8645 8.6756 p. c. of Sulphur in Coke (of Coal.) 22.5401 p. c. of mineral matter. This amounts to 34.0871 p. c. in the Coke. The composition of the Coke then is : Carbon = 58.3600 p. c. Hydrogen = 1.4S33 p. c. Oxygen = 5.5363 p. c. Nitrogen = 0.5333 p. c. Mineral matter == 31.0871 p. c. 100.0000 The relative composition of the organic matter of Coal, Coke and volatile matter, in percentages, is appended here : Coal: Carbon = 50.7400 = 79.19 = 80.30 Hydrogen = 3.9001 = 6.09 = 6.18 Oxygen = 8.5492 = 13.34 = 13.52 Nitrogen = 0.8860 = 1.38 ToOTO 64.0753 100.00 UNIVERSITY OF THE STATE OP MISSOURI. 169 Coke : Volatile Matter : Carbon = 38.5971 = 88.52 = 89.30 Hydrogen = 0.9808 = 2.25 = 2.27 Oxygen = 3.6709 = 8.35 = 8.43 Nitrogen = 0.3526 = 0.88 100.00 43.6014 100.00 Carbon = 12.1429 = 59.31 = 60.89 Hydrogen = 2.9193 = 14.26 = 14.60 Oxygen = 4.8783 = 0.5334 = 23.83 = 2.60 100.00 = 24.51 Nitrogen 100.00 20.4739 I will point out that in calculating Nitrogen and Oxygen in vola- tile matter, as Ammonia and Water, the remaining Carbon and Hydro- gen exist, in equal atomic proportions. Some further experiments were made to test the accuracy of the analytical results, given in the previous part of this paper, first with the Coal, washed with water and subsequently dried, (obtained sub. A. 5,) and then with this Coal, after treatment with Hydrochloric Acid. The results are recorded sub C and D. C. COAL AFTER WASHING WITH WATER. Water removed from the original Coal, as stated sub A. 5, 10.3584 p. c. of solid matter with 5.4059 p. c. of Ash, leaving in the washed Coal 12.2151 p. c. The quantity of Sulphur found was 11.8046 p. c, of which 2.3230 p. c. were removed by water, leaving 9.4816 p. c. behind. The insoluble Residue amounted to 2.9391 p. c. 100 gr. of Coal would be reduced by washing and drying to 84.1683 gr., so that a correction must be made, if we desire to compare the calculated figures with those obtained by actual experiment. By this, we should expect to find in the washed Coal — 14.513 p. c. of Ash. 11.265 p. c. of Sulphur. 3.552 p. c. of insoluble matter (Clay.) CR— 12 170 UNIVERSITY OF THE STATE OF MISSOURI. Water 1. Proximate Analysis of Washed Coal. = 1.841 p. c. 1.224 p. c. 3.965 Mean = 1.532 p. c. Volatile matter 32.421 p. c. 32.303 p. c. 64.724 Mean 32.362 p. c. Ash = 12.851) p. c. 12.934 p. c. '< 25.784 The composition is therefore : Mean = 12.S92 p. c. Water = 1.532 p. c. for dry coal. Volatile matter = 32 362 '• = 32.866 p. c. Fixed Carbon = 53.214 " = 54 041 " Ash = 12.892 " = 13.093 " 100.000 100.000 The ash treated with Hydrochloric Acid left a residue of 3.446 per cent., equal to 3.499 per cent, of the dried coal. The washed coal was dried at a comparatively low temperature, a process which required several days ; the remaining moisture was then determined as described be- fore, and the coal exposed over concentrated Sulphuric Acid, and subsequently to a dry and hot current of air. It lost — 0.469 p. c. in 4 days. 0.510 ' in 9 " 9.459 ' in 16 " 0.348 ' in 24 " 0.800 ' after heating 2 hours. 0.S15 ' after heating 6 hours. It will be seen that the difference between the loss in water and the absorption of Oxygen, which takes place under these conditions, neutralize each other after a while, so that reliable results cannot be obtained in this way. 2. Determination of Sulphur. Total Sulphur = 9.98S2 p. c. of coal. = 10.1436 " of dry coal. In comparing the percentages calculated with those actually found, we are struck by a significant difference between the two sets of figures : Calculated. Ash = 14.513 Sulphur = 11.265 Clay = 3.552 Found. Difference. 13.093 1.420 10.144 1.121 3.4U9 0.053 UNIVERSITY OP THE STATE OF MISSOURI. 171 I was UDable for a long while to account for this apparent dis- crepancy, amounting in the case of the Ash to 10.84 per cent., and in that of the Sulphur to 11.05 per cent, of the coal, but am inclined at present to ascribe it to an oxidation and consequent increase of the coal by drying. It has long been known that coal increases in weight by weathering, which increase will sometimes amount — especially if the temperature be elevated — to about 20 per cent, of the weight of the coal;* at the same time the heating power diminishes, caused by a loss of the Carbon and Hydrogen, which are only partially given off as Carbonic Acidf and water, while by far the larger amount is re- tained, and can be determined easily by the air pump.J In follow- ing out the comparison still further, at least as far as the fixed Carbon is concerned, which I think is obtained by proximate analysis under exactly parallel conditions in both coals, we would expect to find in the washed and dried coal 57.63 per cent. (48.504 per cent, in the pro- portion of 84.1683: 100), we obtain actually 54.04 per cent., a loss also of 2.59 per cent., equivalent to 6.46 per cent, of the coal. Ash and Sulphur furnish a basis for calculating the increase of weight in coal, freer from error, than Carbon; adopting then 11 per cent, as the mean increase, we may calculate the actual loss of fixed Carbon at 4.41 per cent., of which 2.59 per cent, is lost by dissipation and 1.82 per cent, by combination; that is to say, 1.82 per, cent, of Oxygen and perhaps Nitrogen have entered into a combination with the organic matter of coal, which cannot be destroyed by simple heat. E. Richters, in the paper already cited, determines in one case the loss of Carbon under the action of atmospheric air and heat to be 2.61 per cent. D. COAL C AFTER WASHING WITH HYDRO CHLORIC ACID. 100 gr. of the previous coal were boiled with Hydrochloric Acid, the solution filtered off and completely removed by washiDg. It had the following composition : 0.6421 p. c. Ferrous Oxide.? 1.4460 p. c. Sulphuric Acid. 0.0256 p. c. Silica. Trace p. c. Magnesia. 2.1137 p. c. *E. Richters. Dingler's Jouru., vol. 190, vol. 193, vol. 195. |F. Varrentrapp. Dingler's Journ., vol. 175, vol. 178. }E. von. Meyer, Journ. f. pract. Chemie, 1872, vol. v., Ueber die in Steinkohlen eingeschlossenen Gase. gNot all the iron was Protoxide. *■'* UNIVERSITY OP THE STATE OF MISSOUKI. The mineral constituents of the Coal had previously been washed away by the water. Weathering, that is moisture and heat, decom- posed a fresh portion of the Sulphuret, and its composition is repre- sented by the Sulphur and Iron found in the solution : 0.6421 FeO = 0.4994 Fe=:0.01783 Atorns=1.00 1.4460 S0 3 = 0.5784 8=0.03615 Atoms=2.03 The Sulphuret was evidently Fe S 2 , which supports my former statement (A. 6) in reference to the excess of Sulphur found in Coal. In calculating the amount of Ash, Sulphur and insoluble residue in the dry Coal, after the treatment with Hydrochloric acid, we obtain with the correction (96.3543: 100). 12.60 p. c. Ash. 9.76 p. c. Sulphur. 2.58 p. c. Insoluble Matter. 1. Proximate Analysis of this Coal. Water = 0.299 p. c. 0.133 p. c. 0.432 mean = 0.210 p. c. Volat. Matter = 32.612 p. c. 32.477 p. c. 65.089 mean = 32.543 p. c. Ash = 12.347 p. c. 12.788 p. c. 26.135 mean = 12.567 p. e. The composition is therefore : Water = 0.216 p. c. for Dry Coal. Volat. Matter = 32.543 p. c. 32.613 p. c. Fixed Carbon = 54.674 p. c. 54.793 p.-e. Ash = 12.567 p. c. 12.594 p. c. 100.000 100.000 The ash, treated with Hydrochloric Acid, left 3.584 p. c. of Kesi- due, or 3.592 p. c. for Dry Coal. Over Sulphuric Acid this Coal lost : —0.025 in 4 days. +0.005 in 9 days, (gain.) —0.060 in 16 days. —0.192 in 24 days. , — 0.055 after 2 hours drying. — 0.060 after 6 hours drying. The quantity of Sulphur found was 9.9437 p. c, or for Dry Coal = 9.8646 p. c. The calculated figures in this case agree almost exactly with the figures found. UNIVEKSITY OF THE STATE OP MISSOURI. 173 Ash. Sulphur. Residue. Calculated = 12.600 9.76 3.58 Found = 12.594 9.86 3.59 This would exclude an increase in the weight of the Coal by dry- ing after washing with Hydrochloric Acid and Water. I am, at present, not prepared to tell whether this be found true, and whether it is caused by a change of condition, or by a shorter exposure to a somewhat more elevated temperature in drying. I close with the hope of finding other chemists join me in this particular kind of inquiry, namely : of determining the composition of the Organic Mat- ter of Coals. [B.J THE WATER-SUPPLY OF COLUMBIA, BOONE COUNTY, MISSOURI ; BEING AN EXPOSITION OF THE ORIGIN OF THE SPRINGS AND SUBTERRANEAN WATER-COURSES OF THE TOWN AND NEIGHBORHOOD, WITH SOME ANALYSES OF CISTERN WATER. The town of Columbia is situated in a belt of country, the mean annual rainfall of which is 32 inches, a remarkable small amount of atmospheric precipitation, compared with that of the southern portion of the State ; this rain constitutes the larger source of the water- supply of the town, as the springs hardly ever furnish a water of suf- ficient purity to serve for culinary purposes; the reasonof thisisfound in the absence of hills of sufficient height and extent, to collect the waters of an extended area, and in the prevalence of dense surface deposits, such as Bluff (red clay) overlying either Limestones, beds of more or less impure Coal or both. The atmospheric precipitates, which never descend here in profusion at any time, are partly absorbed or sucked up by these formations, and find their way to lower levels by slow degrees, becoming saturated with the products of solution or decomposition of the strata, through which they pass. They appear again in the valley below, either diluted by waters that flow through fissures and cavities in the rock at a more rapid rate, or modified by the last formation, through which they force their way up to light. While there is therefore danger in using the harder water of the springs, from their liability of producing bowel complaints of an aggravated character, there is hardly less danger from using rain water, from its liability of becoming impure. Summer and fall are usually dry; the water gets low in the cisterns and the atmospheric conditions become favorable to the decomposition of Organic Matter, swept into the cisterns from the shingle-roofs of the houses in the shape of dust, leaves, berries and insects. Animal life, microscopic and otherwise is developed, and the mainstay of our health, comfort and civilization, naturally pure water, is put in question. Care and judgment in the selection of spring waters, and supervision of the cistern will however remove all difficulties. In tracing the origin of most of our springs to certain chemical processes, which take place in some of the geological strata, it be- UNIVERSITY OP THE STATE OF MISSOURI. 175 comes necessary to know exactly their composition. I shall give these first ; then describe an experiment to determine the combination in which Iron exists in certain mineral waters, and finally state expe- riments and analytical results of artificial and natural waters in sup- port of my proposition. A. COMPOSITION OF THE BLUFF, LIMESTONE AND COAL. 1. Bluff {Red Clay.) This formation is so well described in the 1 and 2 Report of the Geological Survey of Missouri by G. 0. Swallow, that I concluded to copy the description. The Report: The geological position of this formation in the series of Missouri rocks is easily determined. That it is newer than the drift, is satisfactorily proved by the fact, that it rests upon the latter formation, when both are present and undisturbed. It caps nearly all the bluffs of the Missouri and Mississippi within our State, forming the very highest deposits skirting their valleys. Thus, while the Bottom Prairie occupies a higher geological horizon, the Bluff is usually several hundred feet above it in the topographical. This formation, when well developed, usually presents a fine, pul- vurent, obsoletely stratified mass of light grayish- buff, silicious and slightly indurated marl. Its color is usually variegated with deeper brown stains of oxide of Iron. "When but sparingly developed, it gen- erally becomes more argillaceous and assumes a deeper brown or red color, as on the railroad, south of Palmyra, where it is a dark brick- red, tinged with purple. In some places the ferruginous and calca- reous matter increases, and we find concretions of marl and iron-stone, either disseminated through the mass, or arranged in horizontal belts. At other places it has more arenaceous matter, and is much more decidedly stratified, as at a point one mile above Wellington and in the Bluff at St. Joseph. The Bluff formation is often penetrated by numerous tubes or cyl- inders, about the size or thickness of pipe stems, some larger and others smaller. They are composed of clay, carbonate of lime and oxide of Iron, being argillo-calcareous oxide of Iron or calcareous clay-ironstone. But it is not so easy to say how they are formed. Sev- eral facts may aid us in determining this matter. These tubes pene- trate the formation in all directions, and are most abundant near the surface ; though some extend to the depth of twenty feet. The space of some half inch around each tube-, more or less, according to its size, is of a much lighter color, as if the coloring matter (oxide or Iron) had been extracted. 176 UNIVERSITY OP THE STATE OF MISSOURI. The same appearances were observed around the green and dry roots of the white oak, which had penetrated the same formation Qualitative Analysis proved these same roots to contain a large por- tion of oxide of Iron. And besides, oak-wood always contains a large portion of that metal and manganese. An analysis of its ashes by Saussure, gave 2.25 per cent, of the oxides of these metals; while the analysis of oak-wood-mould, or the decayed wood, by the same Chem- ist, gave 14 per cent, of the same oxides. It is thus made manifest, that oak-wood contains Iron, which must have been absorbed through the roots from the earth. This fact rea- dily explains the loss of the Iron from the marl around the roots, and around the tubes, provided they were once oak-roots. But the ques- tion naturally arises, how these roots become tubular. But they were seen in the various stages of decay, and the woody fibres of some had disappeared, and left the bark in the form of a tube, still retaining its organic structure, though strongly impregnated with the oxide of Iron and aluminium and carbonate of lime. These phenomena have been thus minutely investigated, not merely as interesting scientific facts, but also as one of the most use- ful agricultural features of this preeminently valuable formation ; for upon it, and sustained by its absolutely inexhaustible fertilizing re- sources, rest; the very best farms of the Mississippi and Missouri val- leys. These tubes, and holes, also, constitute the most thorough sys- tem of drainage imaginable. So far as my own observations extend, this formation caps all the Bluffs of the Missouri, from Council Bluffs to its mouth, and those of the Mississippi from the mouth of the Des Moines to that of the Ohio, and forms the upper stratum beneath the soil of all the high-lands, both timber and prairie, of all the counties north of the Osage and Missouri, and also St. Louis and the other Mis- sippi counties on the south. Its greatest development in this State is in the counties on the Missouri, from the Iowa line to Boonville ; but thence to St. Louis it is not so thick. In some places it is two hundred feet thick ; at St. Joseph it is one hundred and forty ; at Boonville one hundred, and at St. Louis, in St. George's quarry, and the Big Mound, it is about fifty feet thick, while its greatest thickness observed in Marion county was only thirty." (So far the Keport.) The specimen which I selected for Analysis came from a shaft, sunk for the purpose of building a cistern, and was taken from a depth of about 12 feet. A large quantity of it was pulverized and air-dried. It had a specific gravity of 2.510 and absorbed weight for weight 0.513 UNIVERSITY OP THE STATE OP MISSOURI. 177 parts of water, so that a cubic foot of it, weighing about 160 pounds, is able to absorb and retain against the law of gravitation 82 pounds of water. This is a significant and important fact to Agriculturists, which I shall discuss more specially at a future time. The Mechanical Analysis or separation of the particles into vari- ous degrees of fineness, executed by a Shone-Apparatus with a fall of water of two feet, gave the following result : 44.372 p. o. coarser particles. 16.155 p. c. finer particles. 16.105 p. c. still finer particles. 16.182 p. c. finest particles. 5.736 p. c. water. 100.000 The coarsest particles were about as fine as fine sand, and probably about six times as fine as ordinary sea sand. No coarser material was found at all. Chemical analysis established the following composition : 77.7061 Silica. 3.0772 Ferric Oxide. 0.2314 Manganic Oxide. 10.2391 Alumina. 0.3788 Lime. 0.2722 Magnesia. 1.5250 Soda. 0.5750 Potassa. 0214 Phosphoric Acid. 0.6426 Carbonic Acid. 5.7363 Water. 100.4051 Another portion was treated with boiling Hydrochloric Acid, and the filtrate analyzed, which, by subtraction from the original analysis, furnished the composition of the insoluble portion. Soluble portion. Insoluble portion. 0.1244 77.5817 Silica. 2.5471 0.5301 Ferric Oxide. .2314 none Manganic Oxide. 3.9251 6.3140 Alumina. 0.2067 0-1721 Lime. 0.2549 0.0173 Magnesia. 7.2896 84.6152 0.0214 Phosphoric Acid. 2.1000 Alcalies. T.3UO 86.7152 178 UNIVERSITY OP THE STATE OP MISSOURI. Two specimens of the same substance, one from the neighborhood of Hannibal, and the other from the Big Mound, St. Louis, were col- lected and analyzed about twenty years ago by Dr. Litton, and show a marked similarity with my sample. They differ, however, from mine in containing more Carbonates of Lime and Magnesia, amount- ing to about 7.5 p. c. in the former and 6 p. c. in the latter. This may be owing to his specimens having come from nearer the surface, where surface waters might have deposited these salts. I will call attention to the Loess, a similar formation to the Bluff, on the Rhine, in Germany, which has a composition almost exactly like that of the Bluff, except in being richer in Carbonate of Lime and Magnesia. 2. Limestone. I quote again from the above Report: This (the Encrinital Lima- stone) is at once the most extensive and best characterized of the divisions of the Carboniferous Limestone. It is made up of brown, buff, gray and white, coarse-crystalline, heavy-bedded Limestones. The darker- colored, impure varieties prevail near the base, while the lighter and more purely calcareous strata abound in the upper part. It everywhere contains globular, ovoid and lenticular masses of chert disseminated or arranged in beds parallel to the lines of stratification. These masses of chert are more abundant in the upper divisions. The beds of this formation are frequently intersected by joints resembling the sutures of the cranium, which I have ventured to call suture-joints. The remains of Crabs and Mollusks are very abund- ant; some of the strata are made up almost entirely of their exuviae, especially of the joints and plates of the Crinoideans. The lower beds are more impure, darker-colored and contain fewer fossils than other portions. Many caves have been observed in these Limestones; several in Boone county were explored— one for the distance of some two miles. They abound in beautiful Stalactites and Stalagmites. Some have streams running along their beds, and constitute a natural system of drainage for a considerable extent of country. " Sink-holes," funnel- shaped depressions, are common in all places where this formation is well developed, and form the natural channels by which much of the surface water reaches the caverns below. Small streams sometimes enter them and again appear at the mouth of the cavern. These "sink-holes" frequently become ponds by the closing up of the pas- sages to the caverns below, with clays impervious to water. There are several such in the western part of Boone county. The thickness UNIVERSITY OF THE BTATE OP MISSOURI. 17& of this formation is quite variable ; on the Osage it is about 200 feet ; on the Mississippi, above Hannibal, 175 feet ; and on the Hinkston, in Boone county, about 400 or 500 feet. There are eight divisions of this Limestone in Missouri, each quite well marked by its fossils. The middle portions of the Encrinital Limestone are made up of thick-bedded, gray and buff and brown, crystalline, crinoidal, cherty Limestones, marked with many suture-joints. This part of the forma- tion is conspicuous in the bluffs of the Missouri, both above and be- low Rocheport, in Boone and Howard counties ; also, on Salt river, in Monroe, where it furnishes an abundance of good building material. The foundations and columns of the State University are from these- beds, as are also those of the beautiful court house in Boone county* (So far the Report.) The composition of this Limestone is : 55.3006 p. c. Lime. 0.4000 p. c. Magnesia. 0.1013 p. c. Ferric Oxide. 0.0946 p. c. Alumina. 0.0019 p. c. Sodium. 43.4505 p. c. Carbonic Acid. 0.3149 p. c. Silica. 0.0021 p. c. Phosphoric Acid. 0037 p. c. Chlorine. 99.6696 Bases and Acids are united in this way : 98.7467 p. c. Calcium Carbonate. 0.8390 p. c. Magnesium Carbonate. 0.0046 p. c. Calcium Orthophosphate. 0.1013 p. c. Ferric Oxide. 0.0946 p. c. Alumina. 0.0056 p. c. Sodium Chloride. 0.3149 p. c. Silica. 100.1067 The specific gravity of the Limestone is 2.682 and it absorbs by weight 0.379 parts of water; a cubic foot of it, weighing about 170* pounds, absorbs 65 pounds of water. As the waters of several springs were supposed to derive their mineral matter almost exclusively from Limestone beds, a large quan- tity in coarse powder was washed repeatedly with distilled water, and the solution analyzed; the Carbonic Acid was not determined directly, but was supposed to be present by absorption from air. 180 UNIVERSITY OP THE STATE OP MISSOURI. Grains in a Gallon. 0.3939 Silica. 2.9427 Calcium Carbonate. 0.8399 Magnesium Carbonate. 0.0234 Ferrous Carbonate. 1.4553 Sodium Chloride. 5.6552 Carbonate of Magaesia and Chloride of Sodium, it will be seen, ■are easily washed out of the Limestone, and this is no doubt the •source of these two salts in many springs and cistern waters. For completeness sake I will give here also the analysis of Chert, accom- panying this Limestone. The fresh mineral has a dark, semi transpa- rent appearance, which, however, changes by exposure to air to an opaque porcelain like color, breaking up at the same time into numer- ous pieces. This change is probably caused by the removal of Alcali and the absorption of water. The unaltered chert contained 0.571 p. c. •of water, while the opaque, weathered specimens contained 0.815 p. c. Chert. 0.5710 p. c. "Water. 95.2910 p. c. Silica. l.OISi p. c. Alumina. 0.0206 p. c. Ferric Oxide, 0.4350 p. c. Lime. 0.3090 p. c. Magnesia. 97.6400 2.3600 p. c. Alcalies (?). 100.0000 S. Coal. For the complete composition of the Coal of this formation, I refer to the previous paper, and confine myself here exclusively to the consideration of the solution obtained by washing this Coal with water. The composition of the solution has been given before, and as it is customary in the United States to calculate the mineral matter of waters in grains per U. S. gallon of 241 cubic inches. I have done it in this case, with the following result : Grains in U. S. Gallon. 0.4258 grains Silica. 55.0412 grains Ferric Oxide. 8.3996 grains Alumina. 169.5829 grains Ferrous Oxide. 18.7974 grains Lime. 0.8374 grains Magnesia. 4522.9250 grains Sulphuric Acid. 576.0093 UNIVERSITY OF THE STATE OF MISSOURI. 181 Bases and Acids were supposed to be united in the following manner: 0.4258 grains Silica. 137.6030 grains Ferric Tersulphate. 27.9714 grains Aluminum Tersulphate. 358.0083 grains Ferrous Sulphate. 45.6508 grains Calcium Sulphate. 2.5222 grains Magnesium Sulphate. 3.8378 grains Sulphuric Acid. 576.0093 It will be seen, that there is an excess of Sulphuric Acid in the- water, as there is likely to be, whenever the products of the decompo- sition of pyritiferous formations do not find sufficient Iron, Lime or Magnesia to unite with. It is in fact artificial concentrated Mine or Pit Water, such as would naturally form in a Coal bed, when water and atmospheric air have access to it. I will place side by side with this three other waters, having the same origin, two of them being waters collecting in Coal mines ; and the third, the water of a spring,, issuing not far from a Coal field in Nova Scotia. They present, it might be supposed, different degrees of concentration of one and the same solution. The results are in grains per U. S. gallon. l. 2. 3. 4. Silica 0.4258 2.6851 1.4651 0.52' Ferric Tersulphate 137.6030 33.4004 21.8603 none.. Aluminum Tersulphate 27.9714 9.6S97 6.1699 none. Ferrous Sulphate 358.0083 1.2083 none. 4.58 Calcium Sulphate 45.6508 36.2957 38.9924 25.69 Magnesiunl " 2.5222 20.7512 23.5881 9.45. Sulphuric Acid 3.8378 8.8667 none. 0.43 Other Salts 10.0290 14.0160 7.72 576.0093 122.9254 106.0909 48.39 The solution, containing the products of decomposition of pyritif- erous Coal, gave a precipitate by boiling; this was filtered off and analyzed, proving to be entirely Ferric Oxide in the form of a basic salt ; its quantity amounted to— 39.6016 Ferric Oxide, leaving in solution the rest of the Iron with all the Alumina^ 15.4396 Ferric Oxide in solution. 8.3996 Alumina. 169.5829 Ferrous Oxide. 2 Th. Poleck and Brettschneider.— Jahresbericht 1869, p. 1284. 3. E. Willigk .— Dingler's Journ., vol. 195, p. 212. 4. How.— Journ. Chem. Society [2], 8, p. 155. 182 UNIVERSITY OF THE STATE OF MISSOURI. Nearly all the figures given are means from duplicate and often triplicate determination, especially with regard to the FeO. I shall now proceed to describe experiments with regard to obtaining a basis upon which to calculate FeO in solutions, containing both Sulphates and Carbonates. B. ON THE STATE OP COMBINATION' IN WHICH IRON EXISTS IN CHALY- BEATE WATERS. In calculating the results of an analysis of a Chalybeate water con- siderable difficulties are met with in the grouping of the bases and acids; this is especially the case when Sulphates and Chlorides of the Alcaline Earths are present, for then the question naturally comes up whether or no a part of the Iron does not exist as Sulphate or Chlo- ride. In all analyses that have come under my notice, Sulphate of Lime was found to be a never failing constituent, and my experiments, I believe, fully prove its incompatibility with Carbonate of Iron ; a partial decomposition takes place, by which Sulphate of Iron and Car- bonate of Lime are produced, the latter of which is precipitated, un- less excess of Carbonic Acid and high pressure prevent it. No mat- ter whether Carbonate of Iron in solution be brought in contact with Sulphate of Lime, or Carbonate of Lime in solution in contact with Sulphate of Iron, the result is always the same ; the Iron is divided between the Carbonic and Sulphuric Acids, one-fourth of it uniting with the former and three-fourths with the latter. If chemists gen- erally have calculated the Iron as Carbonate, whenever boiling or re- moval of Carbonic Acid by an air-pump produced a precipitate, they have lost sight of the fact that only a portion of the Iron is thus precipitated, while the larger part remains in solution ; and this con- version or selection of acids, of which I have spoken, takes place not in consequence of elevated temperature, but at the moment of mix- ture. A solution of 10 grammes of green vitriol was placed in a bottle of 3 litres capacity, and Lime-water added until turmeric paper turned slightly brown, and a filtered part of the solution gave no precipitate with Ammonia. The bottle was by this time nearly filled with liquid, which held a greenish, quickly-subsiding precipitate of Hydrated Pro- toxide of Iron in suspension; the whole was shaken up and Carbonic Acid was passed through for an hour, when most of the precipitated Iron had redissolved. The clear limpid and colorless solution was then filtered off from the slightremaining precipitate and analyzed. It con- tained: UNIVERSITY OF THE STATE OP MISSOURI. 183 Grammes in the Litre. 3.7948 gr. Sulphuric and 2.7942 gr. Ferrous Oxide 1.0252 gr. Lime. 7.6142 la precipitating Sulphate of Iron with Lime-water Gypsum is formed, which remains for some time dissolved in the liquid in larger quantity than is found to be the case, by experimenting upon the solid substance with distilled water ; Carbonic Acid does not affect the solu- bility, as proved by J. Davy, so that we may take all Sulphuric Acid found to have existed originally in combination with Lime as Sulphate of Lime or Gypsum. This would require 2.6564 gr. of Lime, while there are present only 1.0252 gr.; the difference, equal to 1.6312 gr. of Lime must have been precipitated, and can only have been precipi- tated as Carbonate of Lime. To precipitate however 1.6312 gr. of Lime from its solution as Sulphate would require 2.0972 gr. of Protox- ide of Iron in the state of Carbonate, and as all the Iron present must have been originally Carbonate, the difference, equal to 0.6970 gr. of FeO must still exist as such in the solution. There might perhaps be an objection raised to Carbonate of Lime being precipitated in the presence of Carbonic Acid, while Carbonate of Iron is held in solu- tion ; but the former yields up its Carbonic Acid much more readily than the latter, as I found by placing both of them side by side under a bell jar, with caustic Potash and Potash and Pyrogallic Acid. Car- bonate of Lime separated completely in a few days ; Carbonate of Iron had formed only a slight precipitate after a month, and yielded by boiling a copious separation of Oxide. The composition of the solution then was : 2.0972 FeO as Sulphate of Iron. 0.6970 FeO as Carbonate of Iron. 1.0252 CaO as Sulphate of Lime. 3.8194 The proportion between the Iron as Sulphate to that as Carbonate is exactly as 3:1; we might therefore expect that under the same or similar conditions one-fourth of the Iron present would be precipi- tated by boiling. The experiment was made at the time with a por- tion of the same liquid, which was boiled three successive times, the precipitate being filtered off each timo, dissolved in acid and repre- cipitated and weighed. The second and third precipitate contained, or were altogether, basic salt, as Sulphuric Acid was found in them in 184 UNIVERSITY OF THE STATE OF MISSOURI. larger proportion than was required for the Lime that was mixed with them. 0.7058 FeO = 25.26 p. c. 1 precipitate. 0.1613 FeO = 5.77 p. c. 2 precipitate. 0.0797 FeO = 2.85 p. c. 3 precipitate. 1.8474 FeO = 67.12 p. c. remained in solution. 2.7942 100.00 Another experiment was made by placing aside a part of the solu- tion and filtering off the precipitate which had formed after the lapse of a month, and boiling then the filtrate: 0.7438 FeO = 26.62 p. c. precipitated by standing. 0.1795 FeO = 6.42 p. c. precipitated by boiling. 1.8709 FeO = 66.96 p. 6. remained in solution. 2.7942 100.00 The results of these experiments, it seems to me, prove satisfac- torily my proposition, namely, that Carbonate of Iron is decomposed by Sulphate of Lime ; the reverse, however, is equally true and equally supported by figures. Carbonic Acid Gas was passed through Lime-water, which was kept cool by placing the bottle in snow, until much of the precipitate, which had formed at first, was redissolved. The fluid was then filtered, and with proper precaution — that is, exclu- sion of. air — mixed with a small quantity of Sulphate of Protoxide of Iron. The solution remained clear and colorless. It contained, by analysis, 1.4816 gr. of FeO to the litre. A portion of it was boiled, whereby a precipitate formed, which was filtered off and analyzed; it was perfectly free from Sulphuric Acid, proving the absence of all basic salt, and amounted to — 0.3397 gr. FeO = 23.93 p. c. precipitated. 1.1419 gr. FeO = 76.07 p. c. in solution. 1.4S16 100.00 It seems to me then, that in calculating the results of an analysis of a Chalybeate water, containing much Gypsum, one-fourth of the Iron present should only be counted as Carbonate, and the rest as Sulphate. UNIVERSITY OF THE STATE OP MISSOURI. 185 C. ON THE CHANGE IN THE COMPOSITION OP MINE "WATER, BY" PAS- SING THROUGH BEDS OP CLAY, LIMESTONE, OR BOTH. One of the most important questions in Agricultural Chemistry has been, and still is, the determination of the absorptive power of soils for certain substances in solution. A vast amount of labor and patience has been spent upon solving this point, and a vast amount of material has been collected in the shape of experimental demonstra- tion and analytical data. It has been found that the seat of this ab- sorptive power is to be found in the Hydrous Silicates in the soil ; that it is a chemical and not a mechanical power ; that it is in fact no mere absorption, but an interchange of certain acids and bases in the Silicate, with certain others in the solution. "Of the hosts of chemists whose labors have shed light upon this point, I shall only mention the name of one, Way,* who was the first to clearly point out this fact and prove it by analytical demonstration. I mention all this solely for the purpose of suggesting the possibility to calculate beforehand, the re- sult of treating the aqueous solution of Coal with Clay. 1. Treatment with Clay. The experiment was performed in a glass-stoppered bottle, shak- ing the solution occasionally with an excess of Clay for two days, and filtering through a moistened filter. Measured portions of the liquid were then analyzed, and the results calculated in grains to the gallon : 9.9459 Silica. 0.4375 Ferric Oxide. 15.2409 Alumina. 114 6422 Ferrous Oxide. 44.1522 Lime. 13 8826 Magnesia. 2G9 8486 Sulphuric Acid. 468 1499 Bases and acids were united in this way : 9 9459 Silica. 1 0937 Ferric Tersulphate. 50.7537 Aluminium Tersulphate. 242.0224 Ferrous Sulphate. 107.2268 Calcium Sulphate. 41.6478 Magnesium Sulphate. 15 4595 Sulphuric Acid. 468,1499 ^ Tjo^rTof the Roy. Ag. Soc. 1850, Vol. XI., page 313, and Vol. XV., page 491. Bronner proved the fact before. CR — 13 186 UNIVERSITY OP THE STATE OF MISSOURI. The difference between this and the original solution by direct comparison is as follows : +. 9.5201 Silica. + 6.8413 Alumina. +25.354S Lime. +13 0452 Magnesia. —54.6037 Ferric Oxide = 99.25 per cent. —54 9407 Ferrous Oxide = 32.39 percent. —53.0764 Sulphuric Acid = 16.44 per cent. In comparing the amounts of Protoxides, we find that for the Iron retained, an exactly equivalent quantity of Lime and Magnesia was exchanged. The Sesquioxides are partially exchanged for each other and the rest of the Iron retained no doubt as a basic salt. The large amount of Silica in solution points to the Silicate as the seat of this action. By boiling this solution, there was precipitated only a little Ferric Oxide, and no Alumina or Ferrous Oxide whatsoever: 0.4375 Ferric Oxide precipitated. 15.2409 Uumina in solution. 114.6422 Ferrous Oxide in solution. 2. Treatment with Limestone. In digesting the solution of Coal with Limestone the process will be a more simple one, resulting in the neutralization of the Acid, the removal of Sesquioxides and the solution of some Lime. The experi- ment was performed like the previous one, taking care to retain as much as possible the Carbonic Acid generated. Results in grains per gallon: 1.8372 Silica. 7 5249 Alumina. 127.0401 Ferrous Oxide. 78.7202 Lime. 1.4292 Magnesia. 240.1490 Sulphuric Acid. 456.7066 37.2492 Carbonic Acid. 439.9558 Bases and acids were united as follows: 1.8372 Silica. 25.05S7 Aluminium Tersulphate. 203S6S9 Ferrous Sulphate. 67.7258 Ferrous Bicarbonate. "191.1776 Calcium Sulphate. 4.2876 Magnesium Sulphate. 439.9558 UNIVERSITY OP THE STATE OP MISSOURI. 1S7 The amount FeO in the form of Bicarbonate is 31.4766 grains, while it should be, according to the experiment (described under B), 31.7651 grains. I am inclined to ascribe this difference to to an error in the determination of either Iron or Sulphuric Acid. The difference between this and the original solution, is as follows : + 1.4114 Silica. + 59.9228 Lime. + 0.5918 Magnesia. — 55.0412 Ferric Oxide = 100.00 p. c. — 0.8747 Alumina = 10.41 p. c. — 42.5368 Ferrous Oxide = 2514 p. c. — 82.7760 Sulphuric Aeid= 25.63 p. c. It will be seen that Ferric Oxide is easily precipitated in this way, while Alumina, though no doubt precipitated in time, remains much longer in solution. Ferrous Oxide is partially removed, and would be removed completely and quickly if the Carbonic Acid were allowed to escape and atmospheric air be admitted. In connection with this, I refer again to the previously cited paper by E. Willigk.* By boiling there were precipitated from this solution : 23.9401 Ferrous Oxide. 22.4741 Lime. While there remained in solution : 103.1064 Ferrous Oxide. 7.5249 Alumina. This presents two points of interest — the one, that not quite the calculated quantity of Carbonate of Iron is precipitated ; and the other that the Alumina is not easily removed from waters by simply passing through calcareous strata — the former is explained, I think, by simultaneous precipitation of Carbonate and Sulphate of Lime, which rendered some Sulphuric Acid available for the Iron. In a more dilute solution, I have no doubt, this would not take place. No direct experiments were made, to treat the waters filtered off from the clay, with Limestone or the reverse. The changes in com- position will no doubt be similar to those already pointed out, and could easily be foretold and even be estimated. 3. Natural Waters. I proceed now to give the analyses of a number of natural waters, hich I believe are to be traced to such sources as I have marked out * j; Willigk, ibid. Mine-water lost its acid reaction by standing for three days pranular Limestone ; Chalk effected the same in thirty minutes ; broken up W'therite decomposed quickly and completely all Sulphates in solution. 188 UNIVERSITY OP THE STATE OP MISSOURI. in the previous part of this paper. They are waters originating, I think, in decomposing Pyritiferous Coal beds, and are changed by the quantity and quality of the Geological formation through which they pass before issuing above ground. They are arranged according to the degree of change which they have suffered during this passage, and prove, I think, fully my proposition. a. Bratton Spring. This spring is situated about seven miles north of Columbia, and a mile east of Stephen's station, N. M. R. R. It was analyzed in the fall of 1874, containing then 204.1200 grains of mineral matter to the gallon, while in the spring of the same year it contained only 158.4897 grains. The interval had been remarkably dry, and hence no doubt this increase. The results are as follows : 2.5316 grains Silica. 15.7499 grains Alumina. 18.5847 grains Ferrous Oxide. 38.7852 grains Lime. 5.2438 grains Magnesia. 0.5139 grains So lium. 7932 grains Chlorine. 121 9277 grains Sulphuric Acid, 13.3996 grains Carbonic Acid. 217.5296 13.3996 204.1200 Bases and acids were united in the following manner : 2 5316 grains Silica. 52.4489 grains Aluminium tersulphate. 36.7340 grains Ferrous Sulphate. 2.6320 grains Ferrous Bicarbonate. 64.1926 grains Calcium Sulphate. 15.7314 grains Magnes-iuni Sulphate. 1.307L grains Sodium Chloride. 11.9520 grains Carbonic Acid. 217.5296 b. Columbia Chalybeate Spring. The analysis of this spring was published in last year's Catalogue. I copy it here for completeness' sake. The spring, situated in the Uni- versity campus, has been known to the citizens and physicians of Columbia for years, who have used it with entire satisfaction. I ana- lyzed it during the months of June and July (1873), its water being uniformly of the temperature of 61° F., while the thermometer in the UNIVERSITY OF THE STATE OF MISSOURI. 189 surrounding air indicated often 90° F., proving thereby that it came from a sufficient depth not to be affected by atmospheric changes of temperature. There were contained in one U. S. gallon of 23i cubic inches the following substances : 1.45S2 grains Silica. 0.7872 grains Alumina. 2.4773 grains Ferrous Oxide. 45.0871 grains Lime. 10.4473 grains Magnesia. 7.8036 grains Soda. 86.3743 grains Sulphuric Acid. 27.4220 grains Carbonic Acid. 0730 grains Organic matter. 181.21U0 After determining the amount of Carbonic Acid in the water, bases and acids, in the proportion in which they combine, were cal- culated, the results representing the true composition of the water in one U. S. gallon : 1.458 grains Silica. *0 787 grains Alumina. *5.505 grains Ferrous Bicarbonate. 95.777 grains Calcium Sulphate. 31.342 grains Magnesium Sulphate. 16.224 grains Sodium Sulphate. 14 527 grains Calcium Bicarbonate. 15.517 grains Carbonic Acid. 0.073 grains Organic Matter. 181.210 c Second Bratton spring. The spring issues not far from the other spring of Mr. Bratton, but if originating in the same Coal bed, takes a different course before appearing above ground. Only a partial examination of it was made, and the large quantity of Carbonic Acid not determined at all. 61.0394 Alumina. 40.1685 Lime. 2.2166 Magnesia. 166.1310 Sulphuric Acid. 269.5555 There was no Iron present, and the Magnesia and part of the Lime must have existed as Carbonates. This spring probably took its course * These were the results as calculated two years ago. 190 UNIVERSITY OF THE STATE OF MISSOURI. through fissures or cavities in the Limestone, by which all Iron be- come oxidized and precipitated. d. Well Water. Two waters come in here, one from a well in the University grounds, back of the University building, and the other from a well in the yard of the students' cottages. They are at a distance from each other of about 50 feet, and separated by a street running between them. They are fed by a stream running, I think from west to east. Well in Students' Yard. 1.4057 grains Silica. 0.0058 grains Alumina. 16.8641 grains Lime. 4.5908 grains Magnesia. 1.1189 grains Sodium. 1 6748 grains Chlorine. 20 0724 grains Sulphuric Acid 6.1552 grains Carbonic Acid. 51.8877 Bases and acids united as follow*: : 1.4057 grains Silica. 0.0058 grains Alumina. 34.1231 grains Calcium Sulphate. 5.0240 grains Calcium Bicarbonate, 4.6906 grains Magnesium Bicarbonate. 2.7937 grains Sodium Chloride. 3 2102 grains Carbonic Acid. 61.2531 9.3654 grains Carbonic Acid. 51.8S77 "Well in University Yard. 2.0064 grains Silica. 0.0116 grains Alumina. 18 5452 grains Lime. 4 4772 grains Magnesia. 1.0249 grains Sodium. 1.5339 grains Chlorine. 19.7576 grains Sulphuric Acid. 8.6295 grains Carbonic Acid. 55.9863 UNIVERSITY OF THE STATE OF MISSOURI. 191 Bases and acids united as follows : 2.0064 grains Silica. 0.0116 grains Alumina. 33.5879 grains Calcium Sulphate. 12 1241 grains Calcium Bicarbonate. 14.3270 grains Magnesium Bicarbonate. 2.5585 grains Sodium Chloride. 2.9731 grains Carbonic Acid. 67.6026 11.6026 grains Carbonic Acid. 55.9863 There was no organic matter found in either of these two waters. e. Spring in Nova Scotia. This spring was analyzed by How,* and is situated about 3 kilo- metres west of Stellarton, mentioned before as the place in or near which beds of pyritiferous Coal are worked, giving rise to waters like the one I obtained by washing Coal. This spring passes through dark colored Slates and Sandstones, which are without doubt calciferous and the cause of the change in the composition, which is as follows : 0.63 Silica. 11.55 Calcium Carbonate. 3.67 Magnesium Carbonate. 1.14 Potassium Sulphate. 4.17 Sodium Sulphate. 0.84 Sodium Chloride. 3.55 Sodium Carbonate. 25.55 I might close this paper here with the hope of having proved satis- factorily the connection of springs, containing larger quantities of Iron, Alumina or Sulphuric Acid, with beds of decomposing, pyritifer- ous Coal ; but I will add, as an appendix, a few analyses of spring and cistern waters, which have no connection with Coal beds, and contain only the salts carried into solution by contact with Limestone and Clay. D. APPENDIX. The first of these is a spring situated on the farm of Mr. John W. Harris, furnishing an excellent though, perhaps, hard water. It con- tains, to the gallon : * How. Jour. Chem. Society, p. 176. 192 UNIVERSITY OF THE STATE OF MISSOURI. 1.8374 grains Silica. 1 8258 grains Alumina. 20.9987 grains Calcium Bicarbonate. 3.7331 grains Magnesium Bicarbonate. 7.1162 grains Sodium Chloride. 3.7135 grains Carbonic Acid. 39.2247 The second is the water from a cistern* built of Limestone, and not cemented, having, it is said, a connection with a spring. (Cistern situated near the house in which I live.) It contains, to the gallon : 0.525 grains Silica. 1.301 grains Alumina. 7.277 grains Calcium Sulphate. 3.689 grains Calcium Chloride. 0.971 grains Magnesium Chloride. 2.329 grains Calcium Bicarbonate. 0.023 grains Ferrous Bicarbonate. 2.967 grains Sodium Chloride. 3.450 grains Carbonic Acid. 22.532 The third is a water from a cistern* built of Limestone, and not cemented, and about three months in use. The mineral matter of this water has, no doubt, been dissolved from the Limestone. It contains, to the gallon : 0.718 grains Silica. 0.150 grains Alumina. 1.364 grains Magnesium Sulphate. 7.753 grains Calcium Bicarbonate. 0.279 grains Ferrous Bicarbonate. 2.104 grains Sodium Chloride. 1.103 grains Carbonic Acid. 13,471 The fourth is a water from a cistern, well cemented, and in use about two years. All soluble matter of the cement has, in the inter- val, been washed out, so that the total inorganic matter per gallon is only— 1.8204 grains. This has not been further tested. I have omitted to mention, in any of these waters, organic matter, though series of tests were made *Analyzed and published last year. UNIVERSITY OV THE STATE OF MISSOURI. 193 with many of them. I shall at present only give the relative aver- ages of a few, reserving the details for some future time. A solution of Permanganate of Potassa was used for the purpose, which con- tained, in one cubic centimetre, 0.000064 grammes of available oxy- gen. 250 C. C. of water were experimented upon each time. 2.20 C. C. Permanganate for distilled water. 1.00 C. C. Permanganate for well water, obtained from the wells in University and students' yard. 9.50 0. C. Permanganate for cistern water (a spring opening into cistern.) 15.50 C. C. Permanganate for cistern water (containing only 1.8204 grains of min- eral matter. Even this amount of organic matter is not larger than is found in Oroton water, one of the purest waters supplied to a city. There may, however, be danger in using it, as I have indicated before, es- pecially when, after a dry summer, the organic matter in the cisterns is concentrated. These should, therefore, be carefully cleaned out every fall, and will then furnish about as good potable water as can be obtained anywhere in the Mississippi Valley. Cornell University Library QD 39.S41 Comributionsfrommeja^rato^o^the