May, 1917
T H E J O U R N A L O F I N D U S T R I A L A ,V D E iVGI N E E RI X G C H E .MIS T R Y
( 6 ) W. E. Garrigues (1895). “Claims that 90 Per cent Alcohol Precipitates NHiCl from Gladding Wash,” J. A m . Chem. S O L . , 17, 50. (7) R. De Roode (1895), “Recommends Aqua Regia Method for Purifying Potash Solution and Removal of NH4 Salts without Ignition or HzSOd.” J . A m . Chem. SOL.,17, 46, 86. (8) H. W. Wiley (1897), “Method for Determination of KzO and PzOr in Fodders, etc.,” J . A m . Chem. SOL.,19, 320. (9) C. C. hloore (1898), “Use of Acid Alcohol for Purifying KzPtCla,” J . A m . Chem. Soc., 20, 340. Also see Crookes “Select Methods,” p. 32. (IO) Winton and Wheeler (1898), “Study of Effect of “4C1,” J . Am. Chem. SOL.,20, 597. p (11) F. S. Shiver (1899), “Determination of Potassium as Perchlorate, etc., and Preparation of Perchloric Acid,” J. A m . Chem. Soc.. 21, 33. (12) C. L. Hare (1903), “Use of C a ( 0 H ) z instead of Ammonia and Oxalate,” J . A m . Chem. Soc., 2 6 , 41i. (13) C. B. Williams (1903), “Use of HF t o Decompose Soil for Determining K , ” J . A m . Chem. SOL.,2 6 , 495. (14) E. M. East (1904), “Use of NarSOi t o Remove Ba, Thus Avoiding Cse of NHa.” J . A m . Chem. SOC.,26, 297. (15) F. P . Veitch (1905). “Use of Acid Alcohol, etc.,” J . A m . Chem. Soc.. 27, 56. (16) Karl Regel (1906’1, “Difficulties Due t o Sulfates. Estimates P t after Reduction by M g , ” Chem.-Ztg., 30, 684. (17) Wilcox, Buckley and Archibald (1908), “Solubility of KiPtCla in Alcohol of Various Strengths and in KCl and h7aC1,” J . A m . Chem. Soc.. 30, 749. 118) Breckenridge (1909), “Study of Causes of Low Results in Potash Determination by A. 0 . A. C. Method, Especially Effect of the Heavy Pre1 (1909), 409 and 804. cipitate by Ammonia and Oxalate,” THISJOURNAL, (19) T. E. Keitt (1913), “Study of Effect of Phosphates, ctc., in Potassium Determination,” Bull. 173, South Carolina Agricultural Experiment Station. (20) L. A . Hill (1903), “Colorimetric Determination of Potassium; Use of SnClr,” J. A m . Chem. Soc., 2 5 , 990. (21) Cameron and Failyer (1903), “Colorimetric Determination of Potassium, Use of K I on KzPtCla,” J. A m . Chem. SOC.,2 6 , 1063. (22) C. J. Schollenberger (191 l ) , “Effective Filter Tube,” THISJOURNAL, 4 (1912), 436. (23) W. A. Drushel (1O09), “Volumetric Cobaltinitrite hlethod,” 2. anorg. Chem., 61, No. 1, 137. (24) 0. M. Shedd (1910), “Study of Cobaltinitrite Method,” THIS JOURNAL, 2 (1910), 379. (25) L. T.Bowser (1911). “Qualitative Determination of Potassium as Cobaltinitrite,” J . A m . Chem. Soc., 33, 1566. “Quantitative Determination of Potassium as Cobaltinitrite by Titration of the Precipitate with KMnOd.” J . A m . Chem. SOC.,33, 1752. (26) A. H. Bennett (1916), “Use of Sodium Cobaltinitrite t o Separate Potassium from Much Sodium,” A n a l y s t , 41, 165; Chem. Ahs., 10 (19161, 2334. (27) De Vries (1907), “Study of the Method and Various Sources of Error,” Chem. Weekblad., 4 , 231, (28) W B. Hicks (1913). “Reduces KiPtCla by M g and Weight P t 6 (1913). 650. Formed,” THISJOURNAL, (29) Official Method of Association of Official Agricultural Chemists, U. S. Dept. A g r , Bureau Chemistry, Bull. 107, p. 11. (30) Same in J . 0.A . C . . 1 (1916). 12. DIVISIONO F AGRICULTURAL CHEMISTRY UNIVERSITY O F CALIFORNIA BERKELEY
THE FERTILIZER VALUE OF CITY WASTES 11-GARBAGE TANKAGE. ITS COMPOSITION; THE AVAILABILITY OF ITS NITROGEN, AND ITS USE AS A FERTILIZER’ By P. J. SCHROEDER
Among the various materials now obtained lrom city wastes. none has a greater importance as a fertilizer material t h a n garbage tankage.* I t s importance is far-reaching and is of concern t o every urban resident, for i t is necessary t h a t some disposition be made of material produced in such large quantities in every city, and it is of undoubted benefit t o every resident t h a t this be done with as little cost as possible to t h e city. Rendering for the recovery of grease and preparation of a fertilizer material is the method of disposal which Read before the Fertilizer Chemistry Section of the American Chemical Society a t Kansas City, Mo., April 10-14. 1917. * If considered on the tonnage basis, i t may be necessary to make an exception of stable manure.
513
possesses t o a greater extent t h a n any other the t w o most essential characteristics of any method of disposal, namely, economy and sanitation. The facts on which this statement is based will be presented in a subsequent communication. I t is obviously desirable t h a t the products obtained in this disposal be more generally understood, better appreciated and the fullest possible use made of t h e m in order t h a t they may bring as high a price as possible and t h a t their production be made as lucrative as possible so as t o bring the greatest return t o the community. I n the first paper of this series, “The Composition of Garbage,” the results of the analyses of zoo samples of raw city garbage were presented.’ The average of 7 j of the analyses, made of samples taken through a range of time covering a year, were as follows: Moisture, j 3 . j8 per cent; ash, 3 . 6 0 per cent; oil (ether extract). j .3 2 per cent; potash (K20). 0 . 2 j per cent; phosphoric acid ( P ? 0 5 ) . o 43 per c e n t ; nitrogen, 0 . 70 per c e n t , and combustible matter 22.63 per cent. METHODS O F R E S D E R I K G
For the recovery of grease, garbage is treated in three different ways: I-It is “tanked,” i. e . . cooked under pressure with steam, the water and liberated fats pressed out as completely as possible, and t h e oil separated from this by settling and skimming, the grease remaining in the solid residue after it has been dried being extracted with gasoline. 2-It is crushed t o render the particles uniform in size, dried directly in rotary, hot air kilns. the grease extracted with gasoline, and the solids ground for tankage. 3-It is heated with gasoline t o the boiling point of t h e latter, whereby the water contained is evaporated with the gasoline boiled off, while the grease is being extracted. The material is thus degreased and dehydrated in one operation and in one receptacle. I n some plants where the first-named process is in use, the dried tankage is not extracted with gasoline for the recovery of the grease still remaining therein, t h e operators contenting themselves with t h a t recovered by cooking and pressing. CHAR ACT E R A pi D C 0 MP 0 SIT10 li
Garbage tankage, then, is t h e solid residue when t h e water, the grease, and, generally, the water-soluble portions of garbage have been removed. From the foregoing paragraph it is seen t h a t by the first method mentioned the water-soluble ingredients are removed by cooking in steam and t h e subsequent pressing, while by the other two methods all the ingredients, except those volatilized b y drying and dissolved out by the gasoline, are conserved. I n some cases the aqueous solution pressed from the cooked material in t h e first-named process is evaporated for the recovery of its ingredients. The resulting concentrate is a sticky molasses-like substance known as “stick” and may be added t o the degreased tankage, which is 1
49-54.
W. J O’Brien and John R . Lindemuth, THIS J O U R N A L9, (1917).
5 I4
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
then subsequently redried. The addition of t h e “stick” not only increases t h e proportion‘ of t h e valuable constituents of t h e tankage, b u t materially improves its physical condition. The fibrous portion of t h e substances constituting t h e raw material after cooking, pressing and drying becomes light a n d fluffy and makes t h e tankage quite bulky. T h e application of “stick” corrects this and yields a granular product of increased specific gravity which can be handled more conveniently for fertilizer purposes. I n appearance garbage tankage is a coarse, brown powder, either granular or finely fibrous, depending on its method of preparation. I n it generally can be detected small pieces of bone, crockery and glass, t h e proportion of these depending upon t h e thoroughness with which the various sorts of waste materials have been Segregated in t h e households from which collected and t h e care with which sorting has been conducted in t h e rendering plants. I n some cases glass and crockery are eliminated, while in other plants considerable quantities find their way into the products. When t h e origin’ of garbage tankage is recalled, it is seen t h a t i t is made u p of t h e dried and degreased portions of various sorts of food materials, animals and vegetable, and of waste products resulting from the preparation of food a n d remaining after the more edible portions of food materials have been consumed. I n addition it contains variable b u t generally small quantities of substances of a n inorganic origin. CHEMICAL COMPOSITION
Since, as will be seen subsequently, garbage tankage is of interest a t t h e present only as a fertilizer material (and t o some extent as a cattle food), only those constituents were studied which are of interest from the fertilizer point of view. These are nitrogen (from which protein may also be calculated), bone phosphate, potash, ash, organic matter (by difference), fat and moisture. The methods of analysis employed were those prescribed as official methods for agricultural analyses. The values recorded as fat represent ether extract. Efforts have been made in recent months t o utilize tankage as a hog feed. From t h e results reported from these experiments t h e conclusion may be drawn t h a t as such i t has not been an unqualified success. It is rich in protein and carbohydrate when prepared by modern methods; analyses of several samples show about 19 per cent protein and 45 per cent carbohydrate. These materials are digestible. AS a fattener, it is not all t h a t may be desired, but as a part of a properly balanced ration it gives promise of becoming useful. Tankage prepared for hog or cattle feed is carefully freed from bone and other hard materials t h a t might be injurious t o t h e digestive tracts of t h e animals t o be fed. Flotation methods for effecting this separation have been devised which are highly efficient and show promise of commercial applicability. 1
Cf. O’Brien and Lindemuth, LOC.cii.
Vol. 9 , No. 5
I n Table I are given the results of analysis of 2 0 samples of tankage from various reduction plants. The analyses made, a t t h e time of collection of the samples, represented all t h e larger garbage reduction plants in operation in this country. I n these plants t h e various methods of rendering outlined above were employed; it is possible, therefore, t o observe in a general way t h e effect of method of rendering on composition of the tankage. Among t h e samples analyzed, Nos. 2 , 15, 16 and 17 were dried without cooking as described under ( 2 ) and certain of these, it will be observed, were not degreased subsequently. Samples 14, 18 and 2 0 were tankage prepared by t h e method described under (3) ; i . e . , by drying and degreasing simultaneously with gasoline (the Cobwell process). The balance were tankages produced by t h e old tanking process, described under (I); No. I O was not extracted with gasoline; No. 6 contained the concentrated “stick” water from t h e tanks. The effects of degreasing are shown by t h e samples referred t o , which indicate a n oil cont e n t of approximately 1 2 per cent. This soil is one of t h e most valuable products derived from garbage, especially a t present prices, while its removal from t h e tankage is a benefit from t h e fertilizer view-point. Sample No. 6, containing t h e “stick,” is of interest considering its high content of nitrogen and phosphoric acid a n d especially t h e high percentage of water-soluble nitrogen compared with t h e other samples as shown in Table IV. It will be observed t h a t t h e nitrogen content of these tankages is about 3 per cent. An occasional one exceeds this (cf. Nos. 6 and 19), a fact possibly explainable on t h e ground t h a t in case dead animals a n d meat trimmings, if available only in small quantities, are rendered with garbage, or t h e tankage obtained from t h e m is added t o the garbage tankage, thus slightly raising its nitrogen content. T h e high ash content is t h e product of t h e bone present and t h e various foreign substances, such as broken glass and crockery, which find their way into t h e raw material. PRODUCTION OF GARBAGE TANKAGE
I n 1914there were 2 9 companies and municipalities engaged in t h e rendering of garbage on t h e large scale for t h e recovery of grease and t h e production of tankage. I n t h e aggregate they were rendering 1,200,ooo tons of garbage per year and were producing over 173,000 tons of tankage. This represents a yield of 1 5 per cent tankage. This tankage, not counting t h e value of the grease recovered, represents a value on the basis of prices paid for this maof $1,157,000 terial before t h e beginning of the European War. A t present prices this value amounts t o over $z,ooo,ooo. Only about one-half of the cities of over 30,000 population render garbage for t h e production of t a n k age. Installation of rendering plants in these cities where t h e garbage is not being conserved now would raise t h e annual production t o over 345,000 tons and t h e value t o over $4,000,000in addition t o t h e value of t h e grease obtained from it.
May,
1917
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E V I S T R Y
515
admirably suited, and tends t o encourage the use of totally inert and useless materials for t h a t purpose. Garbage tankage is applied largely t o t h e production of mixed fertilizer, being used as a base. For this State fertilizer laws are designed primarily for the purpose it is well suited. It is in t h e form of a pow- protection of t h e farmer against fraud and should of der and is non-caking, a n d since it has a drying effect course be respected. They should, however, be cono n acidified phosphate rock, it imparts these proper- siderate of all t h e facts. I n excluding garbage tankties t o the mixed fertilizer of which i t constitutes a age from mixed fertilizer, either directly or indirectly, part. While making a n admirable base because of no benefit is secured by any one and a positive injury these characteristics, it contributes its quota of t h e fer- is effected. It is not unavailable nitrogen in t h e same tilizer elements a t t h e same time. It is a fertilizer sense t h a t leather meal is, and it cannot be used as a diluent, so t o speak, or base, b u t is not t h a t in t h e same substitute for high-grade nitrogen carriers, as can sense in which totally inert materials would be. I n leather meal, because it does not contain sufficient addition t o these elements it supplies liberal propor- nitrogen. There does not appear t o be any just tions of organic matter which also plays an important reason then why its use should be discouraged. On r81e in a fertilizer way and is badly needed by many the contrary, the benefits t o be derived by its increased soils. When t h e farmer buys a fertilizer material use justify its indorsement for the purpose to which containing garbage tankage as a base, he is not pur- it is now being applied.’ The small price obtained for garbage tankage is chasing a n d paying freight on t h e large proportion due t o the fact t h a t such a low valuation is placed on its of inert material t h a t he would be in purchasing a ammonia, t h a t being only a fraction of the price fertilizer of t h e same grade containing inorganic assigned ammonia in other tankages. Thus while matter as a base. He would even be justified in paying freight for short hauls on garbage tankage $3. I O per unit was quoted for the ammonia of highgrade ground tankage,2 $3.44 for fish tankage and alone. $ 1 . 3 0 for cottonseed meal, only $1.60 per unit was A certain quantity of garbage tankage has been offered for t h a t of garbage tankage.3 This is due t o used as a complete, low-grade fertilizer, without adthe fact t h a t t h e ammonia of garbage tankage is mixture with more concentrated materials. Its use rated as non-available. in this manner has met with pronounced success in Examination of t h e literature does not reveal exthose cases investigated. I t s cheapness makes posperiments t o determine t h e availability of the nitrosible its use in large amounts so t h a t advantage is gen of garbage tankage of sufficient number and defiderived from its high content of organic matter, or niteness t o justify t h e conclusion t h a t t h e ammonia is the so-called humus-forming constituents. For this non-available. T h a t decision seems t o have been reason its use in this manner should be especially made largely arbitrarily. I n the absence of definite profitable in light, porous soils, constitutionally deproof there seems t o be no reason for taking such a plete in organic matter, since the application of such position as there are no a priori considerations supmaterials improves t h e physical condition of such porting it. I n fact, these considerations rather point soils, increases their water-holding capacity and act o t h e conclusion t h a t the nitrogen should be availcelerates bacterial activity. able. The animal nitrogen is contributed t o meat scraps and bones, t h e vegetable nitrogen by such A V A I L A B I L I T Y O F THE N I T R O G E N materials as t h e rinds of melons, t h e skins of fruits, The principal value of garbage tankage, as suggested the bruised and withered portions of leafy vegetables, above, is in its utilization in t h e preparation of feretc. The treatment of these materials in t h e course tilizers. As such its value is based upon its analysis, of manufacture should contribute t o their disintegraa n d , among its constituents of fertilizer value, nitrotion and aid in making t h e nitrogen more readily gen is of chief importance. As a nitrogen carrier it available. gives promise of becoming one of t h e important sources The difference between present and old methods of t h a t element. The obstacle in t h e way of its exof collecting garbage should also be r e ~ a l l e d . ~I n tensive utilization in t h e past has been t h e question 1 I n this connection it is interesting to quote a paragraph from the of the availability of t h e nitrogen. I n certain quar- statement of the Committee on Fertilizer Legislation of the American ters a prejudice seems t o exist against its use; it is Chemical Society at the New York Meeting, Sept. 25-30, 1916, which reads: “In previous reports we have referred to legislation which discriminates listed arbitrarily with carriers of non-soluble nitrogen. against ammoniates which are known to have a definite value, even though I t is spoken of in connection with leather meal and this status be denied t o them by the present empirical methods of testing t h e idea seems t o prevail t h a t it is similar t o this. for availability of organic nitrogen. Furthermore, the methods of stating the results of analyses in some states are very misleading as to the quality The farmer rightly has been instructed not t o pur- of the nitrogen which has been used. Many of the sources of organic chase unavailable nitrogen; as a result of this t h e nitrogen, which were formerly used for fertilizers, are now utilized for other value of garbage tankage has been rather discounted. purposes and unless fertilizer manufacturers can utilize all such sources as are known to be valuable, or can be made so by chemical processes, the The fertilizer laws of certain states require t h a t t h e prices of organic ammoniates will go so high as to prohibit their use. There source of nitrogen in mixed fertilizer be stated on t h e is a large demand for nitrogen from organic sources and it is the desire of label of t h e container. When such a label indicates manufacturers to meet this demand, but such materials cannot be employed at a cost at which they cannot profitably be used by the consumer.” [See the presence of garbage tankage t h e farmer is naturally Txxs JOURNAL, 8 (1916), 1073.1 * Wholesale prices January, 1914. restrained in t h e purchase of i t because of his instrucCurrent prices for ammonia in garbage tankage range from $2 to tions. This militates seriously even against the use $2.508 per unit. of garbage tankage as a base o r filler, for which it is O’Brien and Lindemuth. LOG.clt. G A R B A G E TANKAGE AS A FERTILIZER
T H E J O U R N A L O F I N D U S T R I A L A-VD E N G I J E E R I N G C H E M I S T R Y
516
former times there was practically no selection of garbage, a n d all sorts of refuse were thrown into this material. Now, however, a selection is made a t t h e point of origin, and a t t h e city collecting stations t h e garbage is carefully sorted; such reEuse as old shoes, tin cans, bottles, etc., is removed and sold as such a t considerably higher prices t h a n t h e weight
Vol. 9 , SO.j
carrier is first thoroughly leached so as t o remove all t h e water-soluble nitrogen a n d t h e n t h e sample, which is so chosen as t o contain j o mg. water-insoluble nitrogen, is digested a n d distilled with I O O cc. of alkaline permanganate solution containing z j grams potassium permanganate a n d 150 grams sodium hydroxide per liter. The nitrogen dissolved in this way,
TABLE I-ANALYSES
h-0.
OF GARBAGETANKAGE FROM VARIOUS PLANTS. RESULTSI N PERCENTAGES The analyses represented in this table were made by John R . Lindemuth formerly of this Bureau All results calculated on moisture-free basis Bone phosphate calculated from PzOs using 2.2 as fact:or NHa calculated from N using 1.2 as factor Oil extracted with Ether SOURCE OF S A M P L E N NHI PzOs BonePhosDhate KzO Ash 2.91 3.49 4.83 10.62 0.27 29.48 2.90 2.35 2.40 0.95 ... 5.17 2.69 3.23 3.83 0.79 8.43 2.95 3.54 6.71 3.05 1.66 2j:ia 2.89 3.47 4.67 10.27 0.39 31.97 3.45 3.77 4.20 0.90 27.92 9.24 2.36 2.57 5.32 11.70 0.59 48.92 3.06 3.34 5.46 12.01 0.48 32.84
2.74 2.74 2.32 2.63 3.20 3.45 2.08 1.74
3.29 3.29 2.78 3.16 3.84 4.18 2.50 2.09
5.94 4.52 2.98 3.99 2.69 1.92 1.37 0.49
13.06 9.94 6.56 8.77 5 91 4.22 3.01 1.08
0.20 0.19 0.76 0.65 1.09 1.29 0.91 0.79
36.iO 29.12
degreased) ......................................... 2.11 18 Bartlett & Snow Co., Exposition Grounds, San Francisco, . _ _ Cal ................................................ 2.821 19 San Francisco Disposal Co., San Francisco, Cal . . . . . . . . . . 4.98 20 Pacific Reduction Co., Los Angeles, Cal . . . . . . . . . . . . . . . . .2.96 AVERAGE ............................................ 2.78
2.53
1.96
4.31
1.06
3.46 5.98 3.41 3.34
3.19 6.i3 l,85 3.56
7.02 14.81 4.07 7.84
0.97 0.81 1.27 0.80
10 11 12 13 14 15 16 17
. .
value in garbage. The presence of this material in t h e old t y p e of garbage tankage went a long way towards condemning its use, and t h e present carefully selected kitchen refuse, consisting mostly of vegetable matter, meat offal, a n d bones, is a n entirely different product from t h e material formerly known as garbage tankage. EXPERIMEN-TAL
DATA
OK
THE
AVAILABILITY
OF
THE
NITROGEIi
I n view of these considerations it seemed desirable t h a t further work be done. The question of t h e availability of t h e nitrogen of a fertilizer is by no means easy of definite solution. I t has been t h e subject of a great deal of research for a number of years,’ b u t has not resulted in much definite knowledge on t h e subject. The methods t h a t are now most familiar a n d regarded as official are t h e alkaline permanganate
Oil 1.93 2.80 1.74 3.83 6.69 2.00 1.86 3.12
Moisture 4.37 3.95
....
3.72 3.14 3.86 2.51 5.44
...
1.64 11.25 4.82 2.08 7.10 2.45 12.09 13.92
2.92 3.48 4.51 3.99 6.67
...
11.22
3.77
...
0.88 3.49 3.49 4.92
3.34 3.67
36:47 20.74 19.42 28.03
25.27 13.63 29.15
3.78 2.36
....
....
in addition t o t h a t soluble in water, is considered as available nitrogen. The results obtained by t h e alkaline permanganate method with t h e principal types of garbage tankage are given in Table 11. Cottonseed meal is taken as a standard. Its position as nitrogen-carrying fertilizer is well known, a n d of t h e various nitrogen fertilizers of recognized availability it seems most comparable t o garbage tankage, t h e former being entirely a n d t h e latter largely a vegetable ammoniate. When t h e relative availabilities as indicated in Table I1 are noted it is seen t h a t only one of t h e tankages falls below 40, while t h e average is only 13 points below t h e availability of cottonseed meal. By referring t o t h e first column of t h e table it will be noticed t h a t t h e samples of garbage tankage necessary t o furnish jo mg. of water-soluble nitrogen ranges from about
GARBAGE TANKAGES AND COTTONSEED MEAL COMPARED BY THE &KALINE PERMANGANATE METHOD I N VARIOUS TABLE 11-AVAILABILITY OF THE NITROGEN Weight of Sample Containing 50 Mg. Water-Insoluble N for Alk. KMnOa Det’n Fertilizer Grams Cottonseed meal.. . . . . . . . . . . . . . . . . . . . . ., . . . . . . . . . . . . . . . . . . . . . . . . . 0.9560 1.9370 Garbage, Penn. Red. Co., Philadelphia, Pa.. . . . . . . . . . . . . . . . . . 2.1010 Garbage, Mun. Red. Plant, Columbus, Ohio,. . . . . . . . . . . . . . . . . 3.2900 Garbage Mun. Red. Plant, Cleveland, Ohio . . . . . . . . . . . . . . . . . . 1.8370 Garbage: Cobwell System, New Bedford, Mass.. . . . . . . . . . . . . . .. . . . . 2.7170 Garbage, Allegheny Garbage Co., Pittsburgh, P a . , . , . . , , , , , , . . . . . . . 2.1370 Garbage, Pacific Coast Reduction Co., Los Angeles, Cal 2.1190 Garbage, Barren Island, New York City.. . . . . . . . . . . . . . . . . . . .
........
AVERAGEFOR TANKAGES.. ........................................
~~~~
“Reports on Nitrogen during Last 10 Years,” Jour. of the A . 0.A . Vt. Agr. Expt. Sta., Bull. 173. a Tms JOURNAL,4 (1912). 438. 1 2
C.
-
~~
2.3056
method proposed b y Jones2 a n d t h e neutral permanganate method, proposed by Street.3 These are described in Bull. 107,Revised, of t h e Bureau of Chemistry, United States Department of Agriculture. Of t h e two, t h e alkaline permanganate method is perhaps t h e more satisfactory. I n this method t h e nitrogen
WATER-INSOLUBLE SOLUBLE BY NITROGEN RENDERED ALKALINEKMnOa SOLUTION -In terms o-f Weight HzO-Insol. N Total N Per cent Per cent Mg. 26.2 52.50 47.82 20.03 11.3 22.60 16.14 11.7 23.40 17.53 27.20 13.6 26.02 16.5 33.00 23.77 30.98 15.5 19.14 24.20 12.1 18.05 23.40 11.7 13.2
26.39
20.09
Sum of Water-Insoluble
N rendered Soluble
b y alk. KMnO4 and Water-Soluble N (In terms of Total N) Per cent 56.82 31.37 47.15 53.02 47.17 47.09 40.07 40.92 43.82
z t o 3 grams, while t h a t in t h e case of cottonseed meal is only one gram. The size of t h e sample has a n important effect on t h e results obtained b y t h a t method. Experiment shows t h a t t h e larger t h e sample t h e smaller t h e availability indicated. It is of course necessary t o gauge t h e size of t h e sample in some manner and t h e manner chosen is perhaps t h e best available; a t t h e same time i t must be admitted t h a t a
T H E f O r R N A L O F I N D C ' S T R I A L AATD ELVGINEERING C H E M I S T R Y
X a y , 1917
fertilizer like t h e one in question with a low nitrogen content a n d a high non-nitrogenous organic matter content is a t a disadvantage b y this method A notable contribution to our knowledge of t h e availability of nitrogen in fertilizers has been made in recent years by t h e s t u d y of their nitrifiability under actual field conditions as well as in t h e laboratory. Many very interesting results have been obtained by this method and published by Dr. C. B. Lipman,' of t h e University of California. The method proposed b y Lipman has not received t h e publicity a n d t h e recognition of the permanganate method, but it is more considerate of our present knowledge of soil processes a n d endeavors t o approximate t h e natural processes t h a t are actually operative in t h e soil and t h a t control t h e assimilation of a fertilizer. I n this method a small quantity of fertilizer is incubated a t constant temperature and moisture content with a definite quantity, usually I O O grams, of fertile soil a n d t h e proportion of t h e nitrogen converted into nitrates is taken as a n indication of availability. The results obtained by this method vary, of course, with t h e t y p e of soil used. I n Table I11 are given t h e results obtained with t h e various tankages when treated with t h e two soil types, sassafras silty loam a n d Norfolk sand. Results with other soil types are comparable with these. TABLE111-AVAILABILITY OF THE ~YITROGEN IN VARIOUS GARBAGE TANKAGES COMPARED TO THATI N COTTONSEED MEAL B Y THE SITRIFICATION METHOD
SILTY LOAM SASSAFRAS
...... . .
Cottonseed Meal Garbage Tankage Garbage Tankage Garbage Tankage Garbage Tankage Garbage Tankage Garbage Tankage Garbage Tankage
No. No. No. No. No. No.
.
1 2.. 3.. 4.. 5.. 6.. X o . 7..
192.3 164.1 169.5 158.6 164.1 159.0 164.6 165.6
6.1 1.2 2.3 2.6 2.7 1.9 2.4 2.5
2.41 0.93 1.48 2.47 1.77 1.76 1.83 1.82
56.82 21.94 34.90 58.23 41.75 41.52 43.20 42.93
-___
NORFOLKSAND
97.3 69.1 74.5 63.6 74.5 64.0 69.6 70.6
24.0 5.0 11.1 15,l 18 9 9.0 17 0 15 7
9.45 3.87 7.25 14.45 12.35 8.45 12.96 11.62
__ __
56.82 23.30 43.61 87.00 74.37 50.42 78.02 69.95
517
b u t t h e per cent nitrified is greater, t h e average of t h e tankages being 6 0 . 9 j compared t o 5 6 . 8 2 in cottonseed meal. Especial attention is called t o t h e relatively high percentage of water-soluble nitrogen carried b y t h e tankages, shown in Table IV. TABLE IV-WATER SOLUBILITY OF THE NITROGEN OF VARIOUSGARBAGE TANKAGES COMPARED TO THAT OF COTTONSEED MEAL NOTE-Total nitrogen and water-insoluble nitrogen determinations in this and following tables were made by L. J. Jenkins of the Bureau of Cbemistry, U. S. Department of Agriculture. PER CENT h-ITROGEN WATERTotal Water- Water- SOLUBLE in InsolSol- NITROGEN S O V R C E OF GARBAGE Sample uble uble % of Total Cottonseed Meal . . . ,, , , , , . . , , , , , , , . . 5 . i 3 5.22 0.51 8.90 Pa. Reduction Co., Philadelphia.. ... . . 2 . 9 1 2.58 0.33 11.34 Municipal Red. Co., Columbus, 0 . .. . . 3.45 31.01 1. O i 2.38 Municipal Red. Co., Cleveland, 0 . .. . . 2 . 3 6 1.52 0.84 35.59 2.72 0 . 7.3 Cobwell System, New Bedford, Mass.. 3 . 4 5 21.15 0.56 1.84 .4Ilegheny Garbage Co., Pittsburgh.. , . 2 . 4 0 23.32 Pacific Coast Red. Co., Los Angeles. , 2 . 9 6 0.62 2.34 20.93 3.06 Barren Island, New York C i t y . , , , , . 0.70 2.36 22,Si
-_
AVERAGE
FOR
GARBAGE TAKKAGES 2 94
_-
~
~
2 25
0 69
23 74
I t will be recalled t h a t t h e water-insoluble nitrogen of t h e garbage tankages rendered soluble by alkaline permanganate, as shown in Table 11, is relatively small in comparison t o t h a t of cottonseed meal. T h e fact t h a t the total availability compares favorably with t h a t of cottonseed meal is due, t o a large extent. t o t h e large percentage of t h e water-soluble portion. This in some cases is higher t h a n t h e other portion. The percentage of water solubility is brought out in Table V , where t h e availability by t h e alkaline permanganate method, t h e nitrification method with sassafras silty loam and Norfolk sand, and t h e watersoluble nitrogen are all compared. For t h e purposes of this table t h e results are calculated t o t h e basis on which t h e values for cottonseed meal, t h e standard, are t h e same for all methods. TABLE\T-cOMPARISON
OF AVAILABILITY O F NITROGEN B Y WATER S0l.UBILITY,ALKALINEPERMANGANATE AND h TMETHODS ~ AS STANDARD COTTONSEED MEAL TAKEN NOTE-For purposes of comparison the percentages in the last three columns are multiplied by factors which raise the per cent in the case of cottonseed meal to the figure representing the availability of cottonseed meal as determined by the alkaline permanganate method (cf. Table 11).
__
AVERAGE FOR TANKAGES 2 . 2 1.72 40.64 13 1 10.13 6 0 . 9 5 (a) T h e quantities of nitrate indicated in the table are over and above t h a t produced in the check.
For purposes of comparison t h e percentages of nitrogen nitrified are multiplied by factors which raise t h e per cent nitrified in t h e case of cottonseed meal t o t h e figure representing t h e availability of cottonseed meal as determined by t h e alkaline permanganate method (cf. Table 11). This factor is 2 3 . 6 in t h e case of sassafras silty loam a n d 6 . o in t h a t of Norfolk sand. The results with t h e first soil show on t h e average a n availability of about 1 6 . 18 per cent less t h a n cottonseed meal. This is a heavy soil and nitrification should proceed relatively slowly. I n t h e case of Norfolk sand t h e conditions are more favorable t o nitrification a n d t h e statement in a n earlier part of t h e paper in regard t o t h e use of garbage tankage in light sandy soils is here in part substantiated. I n t h e case of Norfolk sand only two of t h e samples show a materially lower percentage of nitrate formed t h a n cottonseed meal. The total nitrogen content of t h e tankage is much less t h a n t h a t of cottonseed meal, 1
Agr. Exp. Sta., Berkeley, Cal., Bull. '260; J . Agr. Res., 7 , 47-82.
Cottonseed Meal .... , . . . . . . GarbageTankage, No. I... . GarbageTankage, No. 2 . . . , Garbage Tankage, No. 3 . . . . GarbageTankage, No. 4 . . . . Garbage Tankage, No. 5 . . . . GarbageTankage, No. 6 . . . , Garbage Tankage, No 7... . AVERAGES
FOR
5.73 2.91 3.45 2.36 3.45 2.40 2.96 3.06
8.90 11.34 31.01 35.59 21.15 23.32 20.93 22.87
56.82 31.37 47.15 53.02 47.17 47.09 40.07 40.92
56.82 21.94 34.90 58.23 41.75 41.52 43.20 42.93
56.82 23.30 43.61 87.00 74.37 50.42 78.02 69.95
56.82 72.40 198.00 227.00 135.00 148.90 133.60 146.00
T A N K A G E S .2. . 9 4
23.74
43.82
34.92
60.95
151.56
___---__
A series of experiments on t h e effect of treating garbage tankage with sulfuric acid show t h a t t h e water solubility, and consequently t h e availability of t h e nitrogen, dan be considerably increased: zoo-gram samples of Philadelphia tankage were treated with the various quantities of sulfuric acid (sp. gr. I . 59) indicated in Table V I , a n d agitated for two hours in a ball grinding mill. The use of 60 cc. of acid, which would represent about 800 lbs. acid per t o n , increases t h e water-soluble nitrogen from 0 . 3 3 per cent t o 0 . 6 6 per cent. This represents a n increase in availability of about 16 per cent. Whether such a n acid treat-
~
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
518 TABLE VI-Tiie
EFFECTOF SULFURIC ACIDTREATMENT ON THE AVAILABILITY OF THE NITROGEN I N GARBAGE TANKAOE FROM PENN.REDUCTION COMPANY PHILADELPHIA, PA.
Volume of Sulfuric Acid cc. n 16
30 40 50 60 70 ..
80 90 100
PER CENT NITROG$N r
Total as found 2.91 2.82 2.70 2.48 2.34 2.30 2.20 2.30 2.30 2.10
WatuInsoluble 2.58 2.43 2.23 1.90 1.80 1.64 1.46 1.48 1.47 1.34
WaterSoluble 0.33 0.39 0.47 0.58 0.54 0.66 0.74 0.82 0.83 0.76
CONCLUSION
The examination of t h e various garbage tankages has revealed no important fact t h a t shows t h a t they are unsuited for fertilizer materia!. The position is not taken t h a t it is possible t o determine the value of a fertilizer material definitely by present methods of chemical analysis, but from t h e examination t h e expectation would seem entirely justified t h a t t h e proper use of garbage tankage should give t h e usual results obtainable from medium or low-grade fertilizers. Garbage tankage offers a large supply of nitrogen. At the present time ever-increasing amounts of such ammoniates as cottonseed meal a n d high-grade tankage are being utilized for feeding purposes rather t h a n for fertilizer and there is a growing scarcity of highgrade nitrogen carriers.’ I n view of these facts, t h e wider use of t h e low-grade materials becomes increasingly desirable. The intelligent use of garbage tankage will make available t h e not inconsiderable nitrogen which it is able t o supply t o t h e fertilizer trade and a t t h e same time will tend t o result in a larger conservation of t h e garbage of t h e cities with increased benefit t o them. BUREAUOF SOILS
U.s. DEPARTMENT OF AORICULTURE WASHINWCONv D.
c.
THE IDENTIFICATIoN OF B y W. S.
HUEBARD Received January 29, 1917
DRUGS
Emodin and emodin-like compounds are found in t h e various species of Aloe, family Liliaceae; various species of Rheum, family Polygonaceae; various species of Cassia,family Leguminosae, t o which belongs senna; Xanthoxylum tingoassuiba St. Hil., family Rytaceae; various species of Rhamnus, family Rhamaceae, to which belong cascara and frangula; Rumex ecklonianus Meissn; polygonum2 cuspidaturn Sieb. e t zucc, family Polygonaceae; Xanthoxylum tingoassuiba St. Hil., a native of Brazil, is not very well known a n d apparently not used. R~~~~ e c k ~ o n j a n u s s is an herb indigenous to South Africa where it has been used in medicine Report on the Fertilizer Industry, Federal Trade Commission, Aug., 1916.
Pflanzenstoffe. Wehmer, Jena, 1911. (19101. I .
* Tutin and Clewer. J . Chem. SOC.,97
.
Weight of Sample WATERWATER- Containing 50 mg. INSOLUBLE NITROGEN SOLUBLEWater-Insoluble N RENDERED SOLUBLE BY NITROGEN for Alk. ALKALINE PERMANGANATE Per cent KMnO4 Det’n Percentages in terms of of Total Grams Water-Insol. N Total N 11.34 1.9370 22.60 20.03 13.83 2.0580 21 .oo 18.10 17.42 2.2420 17.52 21.20 21.60 23.39 2.6320 16.54 23.07 2.7780 18.74 20.60 28.70 3.0490 15.25 21.40 33.64 3.4250 20.80 13.80 35.65 3.3790 13.25 20.60 3.4010 36.07 13.15 20.60 36.18 3.7310 13.70 21.40
ment would be economically feasible would depend on various conditions. I n t h e preparation of mixed fertilizer it might be possible t o utilize t h e excess acid by mixing with rock phosphate and thus reduce t h e cost of t h e treatment.
* Die
Vol. 9, No. 5
SUM OF WATERINSOLUBLENITROGEN RENDERED SOLUBLE BY ALK.KMnOc AND WATER-SOLUBLE NITROGEN Percentages in terms of Total N Water-Insol. N 33.94 31.37 34.83 31.93 38.62 34.94 44.99 39.93 43.67 41.81 50.10 43.95 54.44 47.44 56.25 49.90 56.67 49.32 57.58 49.88
t o some extent. It will be noted t h a t it belongs t o t h e same family as rhubarb, as does also Polygonum cuspidaturn’ Sieb. e t Zucc., which is indigenous t o China and Japan. The U. S. Pharmacopoeia, 8th Edition, recognized all species of Aloe, while t h e 9th Edition recognizes only Perryi Baker, vera Lanne and ferox Miller. The U. S. Pharmacopoeia recognizes t h e species frangula a n d purshiana of Rhamnus under t h e names of frangula a n d cascara sagrada; those species of Rheum which come from China a n d Thibet; t h e species of acutifolia and angustijolia of Cassia under the commercial names of Alexandria a n d India senna. A great deal of work has been done on t h e constituents of t h e emodin-bearing drugs, notably by Tschirch and his co-workers in Switzerland and by Power and his co-workers in England. Relerence t o t h e more important work prior t o 1911 may be found in “Die Pflanzenstoffe” (Wehmer). The principal constituents of Aloes as given by Wehmer are aloin, barbaloin, isobarbaloin, emodin, a n d aloeresin. The constituents of Cascara are best given by H. A. D. Jowettz and summarized as follows: (‘I-In addition t o emodin, the presence of which in t h e bark was fully confirmed, a small amount of a substance isomeric with emodin, melting a t 183’ C. was found. Glucose also occurs in t h e bark. “2-NO evidence whatever could be obtained of t h e existence of chrysophanic acid or chrysarobin in t h e bark, or of glucosides yielding on hydrolysis emodin, chrysophanic acid or rhamnetin. ‘(3-It was impossible t o isolate a pure substance corresponding t o either cascarin or purshianin. “4-Attempts t o obtain t h e bitter principle or derivatives of it in crystalline form were unsuccessful. “5-” difference be Observed between the character of the fresh (1 Year old) and of the so-ca11ed bark (3 years “6-The examination of Rhamnus purshianus D. C., and Rhamnus calijornicus Esch. gave identical results. ((7-’ enzyme was which hydrolyzed amygdalin, but when administered in 1%-
doses had no griping physiological experiments made for the purpose of locating the active principle of t h e drug resulted in t h e following: Emodin is not t h e active principle, and exerts very little, if any, of t h e characteristic aperient action of cascara. The active 1 9
Perkin, J . Chem. Soc.. 67 (1895), 1084. Report 47 (19041, of the Wellcome Research Laboratory.
