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T H E J O C R N A L OF INDL'STRIAL A N D ENGIJEERILVG CHEMISTRY
a n d t h e paper. While t h e first paper will probably be of more particular interest t o chemists, this circular, i t is hoped, will appeal t o all those who m a y desire some general information on t h e subject. It will include a t first, only t h e same classes of ink covered b y t h e technologic paper, b u t it is proposed t o revise this circular from time t o time, adding t o i t other classes of ink as rapidly as accurate a n d reliable information about t h e m can be obtained. Anyone who is interested in t h e subject of printing inks, m a y obtain either one, or both of these publications, on application t o t h e Bureau of Standards, Washington, D . C.
Vol. 6 . NO. 8
Although manganese is not generally regarded a s one of t h e essential elements of plant food, nevertheless numerous experiments have shown t h a t its compounds are invariably present in soils and in a large variety of plants a n d animals which necessarily derive their sustenance from t h e soil. T h e fact having been generally proven t h a t i t is universally present i n plants has caused considerable work a n d discussion as t o what function i t performs a n d whether or not the application of some manganese salts will prove beneficial t o plant growth. I n t h e analysis of 2 3 Italian soils of various kinds (sandy, volcanic, clay a n d calcareous), Contino' found t h a t manganese was always present in amounts varying from a trace t o a s much as 0.48 per cent h'fn304, t h e average being 0.17 per cent hlns04. De Sornay2has shown in t h e analyses of 3 j Mauritius soils t h a t t h e manganese varies from 0.03 t o 0.41 per cent, t h e average being from 0 . I j t'o 0 . 2 0 per cent. H e also found t h a t some plants contain considerable manganese in their ash, t h e proportion in t h e natural plants being usually less t h a n 0.01 per cent but is universally present indicating t h a t plants assimilate i t naturally. These results have been confirmed b y Boname3 who found as much as 1.26 per cent of manganese in arrowroot grown in Mauritius soils. I n this country, Sullivan a n d Robinson4 have found t h a t of 26 American soils recently analyzed, all contain manganese (MnO) i n proportions ranging from 0.01 t o 0 . j 1 per cent. The average content is 0 . 2 0 per cent, or about 8000 pounds per acre foot. Gortner a n d Rost5 have found i n a few Nebraska soils t h a t t h e average manganese content is about 0 . 1 1 per cent MnO. Jadin a n d Astruc6 give t h e results of analyses of about 6 j species of plants in which i t is shown t h a t this
element is widely distributed in t h e plant kingdom. T h e amount present was found t o vary with t h e differe n t organs of t h e plant examined. T h e manganese content of different plants belonging t o t h e same family could not be taken a s indicative of t h e average content t o be expected in other members of t h e order. T h e chlorophyll portions were, as a rule, richer i n this element t h a n the subterranean parts a n d t h e percentage was greater in t h e older leaves, especially when t h e fresh weight is taken, b u t often the reverse if t h e ash weight is considered. McHargue' has determined t h e manganese in a variety of plants a n d his results confirm those of Jadin, Astruc a n d others who might be mentioned, t h a t this element varies considerably i n t h e different organs of t h e same plant a n d of course in different plants. Furthermore, Bertrand a n d Medigreceneau2 have found traces of this element in about 60 species of wild a n d domestic animals a n d i t is therefore thought t h a t i t s presence has some physiological significance a n d is not merely accidental as is commonly supposed. Experience has shown t h a t t h e presence of excessive manganese compounds i n t h e soil are very injurious t o vegetation as they act directly on t h e chlorophyll and cause bleaching or yellowing of t h e leaves. For instance, Kelley3 has found, in Hawaii, t h a t certain black lands on which pineapples did not grow well, showed t h e presence of from 2.43 t o 9.74 per cent Mn304 a n d indicated a close relation between t h e manganese content of t h e soils a n d t h e general appearance a n d growth of the pineapples. Other areas in close proximity i n which they thrived, contained considerably less manganese; otherwise t h e soils were t h e same. Moreover, i t was found t h a t when a n a t t e m p t was made t o grow other plants in these soils, there invariably occurred a yellowing of the leaves a n d premature falling of t h e lower ones. His conclusions were t h a t soils t h a t contain over 4 per cent of manganese are not suitable for t h e growth of pineapples. Guthrie and Cohen4 also found t h a t bare patches of grass soil showed 0.2j4 per cent h4n2O3, while other portions of the soil in which t h e grass was growing well, contained much less. N o other differences were found. They suggest t h a t t h e element was present originally in innocuous form which became toxic by oxidation. I t is interesting t o note in both cases t h a t t h e application of soluble phosphates had a tendency t o correct these toxic conditions a n d in t h e case of t h e grass, restored i t s growth. Ewel15 gives another illustration in reporting t h e Tesults of a n examination of a soil which failed t o grow legumes a n d which was found t o contain considerable amounts of manganese compounds soluble in water, more in fact t h a n of lime. I t has been claimed t h a t manganese serves no useful purpose in plants b u t t h a t i t is merely taken from the
Staz. S p e r . Agar. Itol., 44 (1911), 51-55; J . Chem. SOL. (London), 1911, Aii, p. ,649. 2 J . Chem. SOL.(London), 1912, Aii, p. 1089. 3 Exper. Sta. Rec., 2 1 (1909), 7 1 7 . 4 U . S.D.A , , Bur. Soils, Circ. 1 6 , p. 3 ; E x p e r . Sta. Rec.. 28 (1913). 523. 5 THISJOURNAL, 4 (1912), 522. 6 Compl. rend. A c a d . Sci. (Paris), 166 (1913), 26, 2023-24; Expev. Sta. Rec., 29 (1913), 28, 628.
K y . Agr, E x p e v . S l a . Compt. rend. A c a d . Sci. (Paris), 164 (1912). 15, 941-3; 22, 1450-52; Erpeu. Sia. Rec., 27 (1912), 670. 3 Hawaii Sta., Press Bull. 23, 14; R e p t . , 1909, pp. 58-63; 1910, pp. 14-16, 41-43, 45-50. i l g r . Gaz. N. S. T$;ales, 1910, 21, 219-222; 1911, 22, 1, 70; J . Chem. Soc. (London), 1910, Aii, 444; E x p e r . S i a . Rec.. 26, 122. Science, N. Ser., 16 (1912). 339, 2 9 1 ; E x p e r . Sia. Rec., 14, 231.
BUREAU OF
STANDARDS. WASHINGTON
THE OCCURRENCE OF MANGANESE IN KENTUCKY SOILS AND ITS POSSIBLE SIGNIFICANCE B y 0. M . SHEDD
Received April 22, 1914
HISTORICAL
1
2
Aug., 1 9 1 4
T H E J O U R N A L OF I N D S J S T R I A L A N D ENGINEERING C H E M I S T R Y
soil as are some other non-essential elements, a n d from plants finds its way into t h e animal organism. This view has led a number of investigators t o conduct experiments t o determine if manganese compounds would have a n y practical use in agriculture and t h e opinion of t h e majority is t h a t under certain conditions they may have a decided value. From their work with water, sand a n d soil cultures, Salomone,' Stoklasa,2 L e i d r e i t e ~ - ,Katayama,' ~ Loew6 a n d Asos have come t o the conclusion t h a t small amounts of manganese are decidedly beneficial t o some plants, while large amounts are toxic. I n these experiments, the manganese salts used included t h e phosphate, carbonate, nitrate, sulfate a n d others a n d were tried on a variety of plants such as oats, wheat, potatoes, sugar beets, rice a n d a large number of vegetables. I n pot a n d field experiments on different crops, using manganese salts, very favorable results have been obtained provided t h e right quantities are used, b u t here as in t h e above trials, i t has again been demonstrated t h a t large quantities are injurious. Bertrand' has made experiments on a clay soil containing o . o j 7 per cent of manganese soluble in hydrochloric acid a n d 0 . 0 2 per cent soluble in boiling acetic acid. Oats were grown on 2 plots of 20 acres, both of which had t h e usual manures a n d one pure manganese sulfate a t t h e rate of 44 pounds per acre. T h e manganese salt resulted in a gain of 17 per cent of grain a n d 26 per cent of straw. T h e grain from both plots contained t h e same a m o u n t of t h e element. I n plot tests with grain, using different manganese compounds, Stranipellis obtained increased yields due t o their effect, t h e greatest increase resulting from t h e use of the sulfate. R a y a n d PradierYhave found t h a t t h e use of manganese sulfate o n apricots produced a more luxuriant vegetation a n d increased t h e size of t h e fruits. StoklasalO increased t h e yield of sugar beets from 30 t o j o per cent b y adding a b o u t 8 pounds of manganese a n d 4 pounds of aluminum per acre, in the form of sulfates, t o a complete basal fertilizer. T h e assimilable aluminum salt apparently corrected t h e toxic action a n d promoted t h e stimulating effect of t h e manganese. Very good results have been obtained by Boullangerll with manganese fertilizers on potatoes, oats, peas, clover a n d some truck crops. Extending its use somewhat further, Sanning a n d Tosatti12 report results indicating t h a t manganese sulfate tends t o increase the yield of grapes considerably 1
2
Chem. Zentr., 1906, ii,532: J . Chem. SOC.,(London) 1906, Aii, 792. Compt. rend., 152 (1911), 1340-42; J . Chem. SOC. (London), 1911,
Aii, 643. 3 B i d . Zentv., 40 (1911), 531-35; J . Chem. S O L ,1911, Aii. 923. 4 B d f . Cofl. Agr. Tokyo I m p . Univ., 7 (1906), 91-93. 6 I b i d . , 5 (1902), 161-172. 8 I b i d . , 6 (1902). 17?-185. 7 Compt. rend. A c a d . S c i . (Paris), 1 4 1 (1905), 26, 1255-57; Sta. Rec., 17, 954. 8 A f t ; . 6 Cong. Inlev. Chem. A p p f . , 4 (1906). 14-17. 0 E r p e v . Sta. Rec., 22 (19101, 718. 10 Zbid., 26 (1912), 22.5. 11 Zbid., 29 (1913), 838. 81 !bid., $9 (1913), 838.
Exper.
66 I
while McCalluml has obtained remarkable results in t h e growth of potatoes b y preliminary treatment of t h e tubers with manganese chloride. Seed potatoes t h u s treated, while showing no difference in t h e growth of foliage, exhibited a most pronounced acceleration in t h e formation of tubers. Loew a n d others referred t o above, who are connected with t h e Tokyo Imperial University, have for a number of years made numerous experiments in J a p a n o n t h e effect of manganese salts on various crops. T h e y have obtained some very favorable a n d interesting results, especially with rice. Others might be mentioned who have experimented with manganese fertilizers a n d while t h e results of some are indifferent or negative, still those of the majority are favorable. This of course is t o be expected in work of this character, which, being only in its experimental stage, involves m a n y unknown factors such as t h e amount a n d kind of material used, t h e character a n d location of t h e soil a n d t h e crop grown on it. While t h e experiments have covered a wide field a n d included a large number of investigators, it is interesting t o note t h a t identical conclusions regarding t h e use a n d function of manganese compounds in plants have been independently agreed upon b y several of t h e workers. Briefly stated, these conclusions are as follows: I-Small applications of manganese compounds are in many cases beneficial, while large applications are invariably toxic. 2-The presence of manganese plays a very important part in t h e formation of chlorophyll in t h e leaf a n d hence performs a n i m p o r t a n t function in carbon assimilation b y promoting rapid photosynthesis in the chlorophyll apparatus. 3-When small amounts of manganese compounds occur in natural soils, i t is believed t h a t a two-fold function in plant growth is performed. One is t h a t t h e y act catalytically, increasing t h e oxidation i n t h e soil a n d accelerating auto-oxidation in plants, a n d furthermore, t h e y t e n d t o modify t h e absorption of lime a n d magnesia by partially replacing t h e m from insoluble combinations a n d t o exert a direct effect on t h e osmotic absorption of both. 4-That manganese is invariably associated with t h e oxidases in plants a n d stimulates their action has been proven b y Bertrand a n d others, while Loew considers i t probable t h a t very fertile soils are characterized by the presence of readily available compounds of this element. EXPERIMENTAL
As a considerable number of carefully selected soils had been used b y t h e writer in some former work in comparing t h e amount of total sulfur in continuously cultivated soils a n d subsoils with the corresponding virgin samples, it was thought t h a t i t might prove of interest t o use these for total manganese determinations, in order t o find out what effect continuous cultivation might have on this element. A description of t h e locality where the samples were taken, t h e ro1
A r k Sta. Rcpt., 1909, pp. 584-86.
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
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tation a n d number of years of cultivation, together with t h e yields of crops usually produced o n t h e old a n d new land were given in a former publication.’ It is not necessary t o repeat these d a t a here, except it might be stated t h a t in a large majority of instances the soils h a d been continuously cultivated for a considerable number of years a n d no stable manure or commercial fertilizer had been used. T h e procedure used for t h e determination of total manganese was practically t h e same as t h a t employed b y Gortner a n d Rost in their work referred t o above and consisted of what is commonly known as t h e sodium bismuthate method. They have shown t h a t their method which consists in fusing t h e soil with sodium carbonate t o obtain t h e manganese in solution a n d its subsequent oxidation t o permanganic acid with sodium bismuthate gives higher a n d more concordant results on Nebraska soils t h a n Walters’ method i n which ammonium persulfate is employed as t h e oxidizing agent. T h e Walters method2 had, until this time, been regarded as t h e most accurate method, either gravimetric or volumetric, known for this purpose a n d was adopted by Hillebrand3 a n d Washington4 for t h e determination of total manganese in rocks. It is only necessary t o examine t h e results obtained by Gortner a n d Rost t o be convinced t h a t their method is simpler a n d more accurate t h a n t h a t of Walters; in fact Blair6 a n d Brinton6 have recognized t h e superiority of t h e sodium bismuthate oxidation by stazing t h a t “for samples containing not over 2 per cent of manganese, t h e bismuthate is t h e most accurate method known.” T h e method as used in this work is as follows: One gram of soil is intimately mixed with 4 grams of manganese-free, dry, sodium carbonate a n d fused in a 2 0 cc. platinum crucible over a blast lamp until t h e melt is quiet or for a b o u t t e n minutes. T h e liquid mass is t h e n poured into a IOO cc. platinum dish a n d the dish rotated in order t o obtain t h e melt in a thin film, t h u s providing for more rapid solution. T h e melt a n d crucible are t h e n treated with about I O O cc. of distilled water a n d heated on t h e water bath until t h e fused product is completely disintegrated, which requires about a n hour or two. T h e crucible is then removed from t h e dish, a n y adhering solution washed off, a n d t h e mixture acidified with 1 3 0 cc. of 3 5 per cent (by weight) sulfuric acid a n d diluted t o 2 5 0 cc. Should there be a heavy precipitate of silica a t this point it is advisable t o filter, using a Buchner funnel a n d filtering b y suction. This is seldom necessary, however, for in most cases t h e silica does not precipitate t o a n y extent, b u t merely produces a slight opalescence which does not interfere with t h e permanganate readings. One hundred cc. of this solution are t h e n placed in a n Erlenmeyer flask, t h e contents brought t o boiling, cooled, a n d 0.50 gram Baker’s C. P. sodium bismuthate 1
Ky. Agr. E r p e r . Ste. Bull., 174.
2
Chem. News, 8s (1901). 76; 84 (1901), 239. Bull., 411, 116, U. S. Geol. Survey. “ T h e Chemical Analysis of Rocks,” Wiley & Sons, N. Y . , 1910. “Chemical Analysis of Iron.” 7th ed.. p. 121; J . Amcr. Chem. Soc.,
3 4
5
a6, 793. 6
THISJOURNAL, S (1911), 237.
Vol. 6 , No. 8
added. The amount of bismuthate t o be added, of course, depends on t h e quantity of manganese present a n d might vary from 0 . 2 5 gram t o I gram. It is advisable not t o a d d a n y large excess so t h a t t h e bismuth salts will remain in solution. I t has been found t h a t 0 . 2 5 gram of bismuthate is sufficient where t h e manganese content does not exceed 0 . 2 0 per cent. T h e oxidation mixture is t h e n heated just t o boiling a n d continued only until t h e liquid has the true permanganate color, which requires only a minute or two. The solution a t this point may have a slight foreign red color b u t this will disappear on cooling. Excessive heating of t h e solution is t o be avoided as this tends t o destroy t h e permanganate color a n d gives low results. After cooling, t h e solution is made t o its original volume, or I O O cc., shaken thoroughly a n d if a n y bism u t h a t e salts precipitate, i t is allowed t o stand for some minutes in t h e dark until these settle. If i t is found necessary in order t o obtain a clear solution, it can be filtered through properly prepared asbestos, b u t as soon as possible t h e solution is read in a colorimeter or Nessler’s glasses against a standard solution of permanganic acid which has been prepared b y reducing a solution of potassium permanganate in 2 0 per cent (by weight) sulfuric acid b y t h e cautious addition of sulfurous acid, a n d reoxidizing with bismuthate. T h e standard solution should contain about 0 . 2 mg. of MnO per I O cc. F r o m t h e ratios t h u s obtained, t h e quantity of manganese in t h e original sample is calculated. T h e writer in this work used a Duboscq colorimeter a n d t h e standard was prepared as described above a n d compared every d a y with a freshly prepared potassium permanganate solution, I O cc. of which = 0 . 2 mg. MnO. The standard permanganic acid solution was found t o deteriorate gradually in strength a n d as a potassium permanganate solution of t h e same manganese strength was found t o have t h e same color, a factor could be used on t h e true standard. T h e potassium permanganate standard could just as well be used as a standard b u t as i t was thought best t o have both t h e standard a n d unknown solution prepared in t h e same manner, t h e permanganic acid standard was employed throughout the work. It might also be mentioned here t h a t a potassium permanganate solution of this weak strength gradually deteriorates, so the plan followed was t o make the permanganate solution daily, b y t h e proper dilution of a N / I O solution, a n d t h e permanganic acid standard, every four or five days. I n both, boiled distilled water was used t o which a few drops of weak permanganate were added until just faintly colored. Gortner a n d Rost used t h e permanganate reduced with sulfurous acid as a stock solution which t h e y found t o be stable a n d from which t h e y made their standard as needed, b u t the writer prefers t h e other plan since the exact strength of t h e standard can be determined with very little trouble. T h e method has given very good duplicate results on independent fusions while i t might be mentioned t h a t blank determinations showed no manganese present in t h e chemicals used.
Aug., 1914
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
In t h e following tables, t h e samples in which t h e results are strictly comparable, both in the surface a n d subsoil of the virgin a n d cultivated areas, are given TABLE I-TOTAL MANGANESE IN KENTUCKY SOILS RESULTSIN PERCEN-
TAGSS A N D POUNDSPER ACRE EASTERNCOALFIELIIS AREA SURFACE SOIL SUBSOIL Virgin Cultivated Virgin Cultivated No. COUNTY % Lbs. 70 Lbs. 70 Lbs. % Lbs. 669-72 . . . . . . . Wolfe 0.152 3040 0.072 1440 0.122 2440 0.054 1080 700- 1. . . . . . . M a g o 5 n . . . . . 0.077 1540 . . . . . 0.051 1020 702- 3 . . . . . . . Johnson . . . . . 0.050 1000 0.031 620 704- 5 . . . . . . . Johnson 0.068 1360 . . . 0.076 1520 763- 4 . . . . . . . Johnson 01050 1000 0.009 180 . . . . . 706 . . . . . . . Floyd 0 148 2960 . . . 0:078 1560 0.067 1340 0:063 1260 O:Oj6 720 707-10 . . . . . . . Perry
