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in every case but one-that of the soap from rape seed oil. The same soaps mixed with active agents, namely, a rather high-boiling t a r acid and a solution of caustic potash, h i d entirely different effects on the germicidal values from what one would expect. The extended tests on these lines were carried out using only two of the glycerides, trilaurin and triolein, as represented b y cocoanut oil and olive oil, because these showed wide variation in their germicidal values without added ingredients and because of the limited time to complete the tests. Table IV, here shown, is a compilation of the results obtained from tests of these two soaps used: First, alone. Second, with cresylic acid. Third, with alkali (KOH). Fourth, with both. Tests were also made for the value of the alkali alone, and of the alkali and cresylic acid together. The columns headed “Coefficients,” Table IV, show the number of times the preparation can be diluted compared with carbolic acid, and retain a n equal efficiency.
Aug., 1911
erable light on the subject and explain many of the discrepancies which now appear to make the literature untrustworthy. One point should be noted, that bacteriologists have not used the same organism in making their tests. It is a well known fact that bacteria differ greatly in their resistance toward germicides, B. typhosus being killed by some germicides in a dilution 4 t o 5 times as high as that required to kill B. pyocjianeus. Another point of importance is the effect of hydrolysis on the germicidal value of the soap solution. The table (Table V) here given is for comparison of the values of a dilution when freshly made and again. after 18 hours standing. TABLEV. Olive oil soap and cresylic.. Same after 18 hours . . . . . . .
1-300 1-300
-
+
-
+
-
+
-
-
This shows an evident deterioration probably on. account of chemical changes in the solution. SUMMARY AND CONCLUSIONS.
B. . typhosz~s is especially susceptible to the germicidal action of alkali ( K O H ) . 2 . The combination of soap with an active agent T A B L E Iv. does not invariably enhance the germicidal value of Olive Oil Soap. the latter. Effective dilution. Coefficients. 7 3. The germicidal value of the combination of soap GermiInsectiGermiInsectiand cresylic acid depends on the glyceride used in Combination. cidal. cidal. cidal. cidal. the manufacture of the soap. One may therefore Soap alone.. . . . . . . . . . . . 1-20 1-100 0.17 5.0 conclude that the soap exerts a distinct influence on Soap and cresylic acid.. . 1-500 1-300 4.0 15 .o 1-50 9.0 2.5 the value of this agent. Soap, cresylic acid, and 4. The germicidal value of the alkali is not inalkali.. . . . . . . . . . . . . . . 1-1000 1-300 8.3 5.0 creased by any combination used in this series of Cocoanut Oil Soap. tests. When combined with cresylic acid, its value Soap alone.. . . . . . 1-40 1-100 0.33 5 .O Soap and cresylic acid.. 1-1000 1-100 8.3 5.0 is one-third that of the alkali alone. Soap and alkali., . . . . . . . 1-1100 1-200 9.0 10.0 j. With our present knowledge o the chemistry Soap, cresylic acid, and of these combinations as i t affects germicidal and in1-300 8.3 15.0 alkali. .... . . . . 1-1000 1-25 3.3 1.25 Cresylic acid and alkali. 1-400 secticidal values, no safe a priori conclusions can be 1-25 10.0 1,25 Alkali (KOH) alone.. . . . 1-1200 drawn. Even a laboratory test to determine these In every mixture above described the ingredients values must be carried out under rigidly prescribed are present in equal proportions and in every case conditions. Variations in the method may easily the dilutions given are for each ingredient. make the greatest differences in the results obtained. The literature on this subject is very contradicBIBLIOGRAPHY. tory Some investigators claim that the soap conKonradi, Archiv. f u r Hygiene, Vol. 44. Reichenbach, Zeitschrift fur Hygiene u . Infections Krankhcitcn, stituents in themselves are valuable and that no Vol. 59. difference exists between those from different glycerJolles, Zeitschrift f u r Hygiene, Vol. 15 and 1’01 19. Behring. Zeitschrift f u r Hygiene, Vol 9. ides. Most of the authors consulted conclude that Serafini, Archiv. fur Hygiene, Vol. 33 alkali, volatile oils, or other germicidal agents must Schrauth and Schoeller, Medizinische Klink., Jahr 6 . be present to give a perceptible value. RosenauI makes the following statement : ‘ I Medicated soaps are for the most part a snare and a delu- [AGRICULTCR.4L EXPER13lEKT STATIOX O F THE RHODEISLAND ST.%TECOLLEGE, KINGSTOX, R. I.] sion so far as any increased germicidal action is concerned; in fact, the addition of carbolic acid and other THE AVAILABILITY OF THE INSOLUBLE NITROGEN I N substances, which have the property of combining CERTAIN COMMERCIAL FERTILIZERS.’ with the soap, seems actually to dimidsh the disinBy BURT L. HARTWELL ASD F. R . PEMBER. Received June 19, 1911. fecting power of t h a t substance.” I t should be noted in this connection that without Much uncertainty exists in the minds of agriculthe closest attention to the preparation of the soap, turists concerning the availability of the insoluble variable results are to be expected. I n fact, varia- nitrogen in commercial fertilizers, because of the tions were observed for which no logical reason could difficulty of recognizing the existence of material of be deduced. It is probable that a rigid chemical low availability, such as leather, garbage tankage, control of the reactions involved would throw consid1 Paper read a t the Indianapolis meeting of the American Chemical c
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“Disinfection and Disinfectants.”
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and peat, after they have been subjected. t o certain in nitrate of soda (see the last two series in the table), processes of manufacture. the total yield was somewhat increased, namely, Since the effect upon plants must be relied upon as from 338.9 t o 3 5 7 . 5 grams. It is believed, however, furnishing authoritative information regarding the on account of the fact that the other nitrogenous value of manurial substances, it was decided to secure materials were less available than the nitrate of soda, by pot experimentation some knowledge concerning that the full requirement for phosphorus was probably the actual value of the water-insoluble nitrogenous fulfilled by that which was added in the general apingredients of certain commercial fertilizers. plication of acid phosphate; and that, practically Of the brands collected during the regular inspec- what was present in the nitrogenous materials was tion of 1908, certain ones which had a fairly high per- without effect, especially on the last crop. centage of nitrogen in organic matter, and which Results from an equal amount of nitrogen in nitrate represented different manufacturers, were selected. of soda, dried blood, and the water-insoluble nitrogen Most of them were potato and vegetable fertilizers, of certain commercial fertilizers (Nos. 1-1 2) : and were the higher-priced brands. Availability of Grams of air-dry crops. nitrogen. They were thoroughly leached with warm water, by -.. decantation and on the filter, t o extract especially B y last the nitrates and ammonium salts, but the soluble Oats oat crop, B Y alk. Source of Oats, Millet, ----with blood KlLInO. organic nitrogen was of course also extracted. The method nitrogen. total. total. Total. residues were dried, the nitrogen determined,I and the 16.7 25.5 None. ............ material used in comparison with dried blood ( 1 3 . 6 2 14.7 23.5 per cent, N) and nitrate of soda, on an equal nitrogen 23.6 43.5 70 ................ 21.6 45.5 1 basis, as sources of nitrogen for oats, millet, and oats 24.3 42.0 grown successively on the same soil. ................ 59 21.2 45.0 2 Optimum amounts of lime, potassium and phos24.2 50.0 74 phorus were provided for each crop in order that the 21.5 51.5 differences in growth might be attributable to differ74 ................1f 7758 .. 50 22 13 .. 30 55 11 .. 00 4 ences in the availability of the nitrogen. J 7 1 . 0 2 4 . 0 5 2 . 5 Eight-inch Wagner pots and a light soil which it 5 ................ 78 (78.5 21.5 55.0 was hoped was naturally deficient in nitrogen, were f 74.5 27.3 49.5 76 6 ................ used. The soil was found t o be less deficient than was 174.5 27.7 49.0 estimated, however, so that the first crop of oats was 25.7 53.0 76 7................ 23.0 56.0 too well supplied with nitrogen t o enable marked 26.0 45.0 . f 78.5 differences in availability to be shown. For the SUC73 8................. 22.5 47.0 (85.5 ceeding crops less nitrogen was used, so that less than r 80.5 21.0 4 9 . 0 9................ 76 the optimum amount should be present in those pots 182.5 22.0 51.0 2 6 . 8 5 4 . 5 which had the uniform application. 83 22.7 53.0 The crop results are given in the accompanying (82.5 22.9 52.5 83 11. ............ table. ' ' .I. 7 7 . 5 24.7 51.0 The addition of an extra amount of lime t o two of 53.0 f 85.0 25.5 81 12. . . . . . . . . . . . . . . . 25.8 51.5 186.5 the pots of soil which received blood increased the 27.5 52.0 total yield of the three crops only from 302 to 305.9 79 Dried blood.. . . . . . . 25.8 52.0 grams. I t is evident, therefore, that the general ap30.0 56.2 Dried blood + extra plication of lime was sufficient. On the other hand, 25.7 45.5 lime . . . . . . . . . . . . . when the regular application of nitrogen in the blood 28.4 58.0 Dried blood (extra 91 . 5 31.3 59.0 amount). . . . . . . . . \ 80 .O itself was incfeased, the total yield rose to 3 4 8 . 2 25.9 64.0 grams, indicating that the general nitrogenous maNitrate of soda.. . . . 27.5 60.0 nuring was not suflicient for the production of max28.5 63.0 Nitrate of soda + -imum crops. If such had not been the case there 29.0 64.5 extra phosphate. . -would be no proof that an opportunity had been The increase over the check pots, caused by the .afforded for the materials under comparison to have general application of nitrogen in the dried blood, .exerted their full effect. Although the leaching would remove all of the has been placed arbitrarily at 80 in the table, because ,soluble phosphorus and potassium there would still of our belief that high-grade blood under conditions -remain much phosphorus in the reverted and insol- favorable to nitrification will cause an average in-uble condition which would exert a n effect upon the crease in crop of about 80, in comparison with nitrate crop unless this element was so abundantly supplied of soda a t 100. It may be seen by comparing the weights of the .as to render impossible any additional influence from this source. I n consideration of this, a very crops grown on the different fertilizer residues, with -liberal application of acid phosphate was made for those from an equal amount of nitrogen in dried blood, .each crop, and yet when 5 0 per cent. more was added that with a few exceptions the availability of the :in connection with the general application of nitrogen nitrogen in them was practically equal to that in blood. This fact should increase the confidence of the 1 The.authors are indebted to JIr J. Frank Morgan for this work. ~
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agriculturist in the quality of the material in the more concentrated commercial fertilizers such as those used in this experiment. I n the following respects the best comparison of the different materials is afforded by the growth of the last crop, namely: the soil itself had become more depleted of its nitrogen; the cumulative effects of three applications of nitrogen were exerted; there was scarcely any evidence that the phosphorus associated with the nitrogenous materials exerted any influence; and the grain was allowed to ripen. On the basis of the last crop, only five of the twelve fertilizers (Nos. I , z , 6, 8 and 9) yielded in each of the two respective pots, less total crop and grain than was produced in either of the pots in which blood was applied. Although the insoluble nitrogen in fertilizers I and 2 , particularly, was less available than the nitrogen in blood, there is reason for the belief that it was largely from bone and meat tankage instead of from such low-grade material as garbage tankage, peat, and leather. The directors of certain northeastern stations announced in March, 1910, their intention t o have the fertilizers collected in 1911 for inspection, examined b y some uniform laboratory method as to the availability of their organic nitrogen ; and they appointed a committee of station chemists t o recommend a method. I t was very opportune that the vegetation results under discussion had already been secured on the insoluble organic nitrogen of certain fertilizers, and that some of the identical material was on hand. This material was submitted, without any information concerning the crop results, t o Mr. C. H. Jones, of the Vermont Agricultural Experiment Station, for the determination of availability b y the alkaline permanganate method. The agreement was very satisfactory, but it was considered unfortunate that probably none of these particular fertilizers were made up of low-grade materials. Subsequently, however, a few decidedly low-grade fertilizers were likewise compared, with gratifying results ; the vegetation tests are not fully completed and will not be published a t this time. The alkaline permanganate method was the one adopted March 4, 1911, b y the agricultural experiment stations of New York, New Jersey and the New England States for “examining the activity of the organic forms of nitrogen,” and a circular was printed which includes the details of the method. I n the last column of the accompanying table we have included the results secured by Mr. Jones with the method as adopted. The agreement is quite good even without full recognition of the fact that the limit of error in vegetation experiments must be placed rather wide. Even the hird crop (oats) equaled 49 grams on the check pots, although the pots to which blood was added yielded j5 grams more; this is taken to represent a range in availability from o to 8 0 ; it is evident, therefore, that even a variation of 3 . 4 grams in the weight of the crop from two parallel pots represents a difference of j in availability.
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With two kinds of crops even on the same soil, the degree of availability will vary considerably, and on different soils the variation may be expected t o be still greater. It is probable, for example, that an experiment with rye on an acid soil, in which the predominating microflora is composed of fungi a n d yeasts, would result in quite a different availability from one with barley on a neutral or alkaline soil in which bacterial growth is the more prominent. Two nitrogenous materials might exhibit very different relative availability, depending upon which of the above-mentioned conditions existed. An availability test even with a single kind of plant and soil may comprise the following: one manuring and one planting; one manuring, and more than one planting; or more than one manuring and as many plantings. I t should be understood, therefore, that a difference of a t least ten per cent. in the availability as determined by pot experiments is not of much significance, especially when no standard conditions have been adopted for carrying on vegetation tests. The degree of availability of a substance, whether determined by vegetation or chemical tests, should be considered only as a n approximation which is useful in distinguishing between materials of quite different qualities.
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T H E NATURE OF SOME COAL DUSTS AND MINE AIR FROM COLORADO MINES. B y JOHN B . EKELEY. Received M a y 2 , 1911
I n November, 1910, Governor John F. Shafroth appointed a commission, consisting of Victor C. Alderson, president of the State School of Mines; James Dalrymple, state coal mine inspector; R. D. George, state geologist and professor of geology a t the University of Colorado; and John B. Ekeley, professor of chemistry a t the University of Colorado, t o inquire into the condition of the coal mines of Colorado, and the causes of the many accidents in those mines, and to suggest remedial legislation for the consideration of the Eighteenth General Assembly of the State. The following tables give the analyses of samples of coal dusts and of mine air taken during the investigation trip made by the Coal Mine Commission. The coal dust samples were passed through 20-, 100-,and zoo-mesh sieves, and the fractions analyzed. I n the fractions passing through the 200-mesh sieve, the analyses show a slight error, because the very fine dust undoubtedly lost some moisture during the screening operation. However, the results for this fine dust are very interesting, because they show that in all cases the composition was approximately the same as in the coarser portions. The analyses show that the non-carbonaceous part of the dust was of about the same state of division as the coal dust itself. The air samples were collected b y allowing water t o run out from completely filled glass bulbs, which were then closed air-tight. This is the method used by Mr. Chamberlin, of the United States Geological Survey. The small amount of water remaining on
