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 C I A T E E R I N G CHEMISZ'RY
420
sulfatc which stick t o t h e glass.) Cool, dilute a n d t i t r a t e a s above. After such t r e a t m e n t t h e blank is 0.35 (instead of 0.4 cc.) for steels with under 0.5 per ccnt C, a n d 0.5 cc. for 0.60 t o 0 . 7 0 C, a n d 0.6 cc. for 0.90 t o 1.25 C steels. Thc blanks are t h e same with or without t h e persulfate treatment for steels of over 0 . j o per cent carbon. T h e ferrous ammonium sulfate solution m a y be standardized against 0.1 N perrnanganatc, t h e strength of which has been determined with sodium oxalate. T h e iron value of the permanganate multiplied b y 0.917gives t h e vanadium value. By this method t h e following results were obtained, t h e chromium in expts. 9, I O , 13 a n d 14 being added a s KzCrlOl before the solution of t h e steel. T h e following steels were employed: A-U. S . Bureau of Standorde Sample h70.24, containing 0.15 per cent V. 11.35 per cent C.and a trace of Ci. B-U. S. Bureau of Standards Sample No. 30, containing 0.21 per cent V. 0.37 per cent C.and 1.35 per cent Cr. C-A steel casting confaning 0.2 I S per cent V. 0.30 per cent C.and no Cr. D--A plain steel containing 0.85 per cent C. Ti-'1 plain steel cootnining 1.25 per cent C.
Vol. 7 , No. 5
investigators a n d their co-workers, we have come t o regard t h e soil organic matter not a s consisting of three of four compounds of rather indefinite properties, b u t a s being made up of a largc number of different organic compounds which result from plant and animal residues through t h e agency of t h e various chemical processes which are taking place in t h e soil. From various soils there have bcen isolated a n d identified up t o t h e present time, more t h a n half 3 hundred definite organic compounds. Among t h c various classes of organic compounds represented are acids, aldehydes, alcohols, amino acids, resins, cster6, glycerides, hydrocarbons, sugars, amines a n d other nitrogenous compounds. T h e methods by which these compounds have been isolated and identified are somewhat involved a n d ncetl not be considered here. The toxic effect on wheat plants of t h e various organic compounds which have bccn isolated f r o m various soils has been extensively srudied by Sclircincr' t h e work a n d his co-workers. With t w o
T A B LI-~IINIDIVM ~ DBTERMZNAT~ONS BY S I M P L ~ MBTXOD ED !%,eight of Persulfate Vanadium ~rmple added lnund EWt. Sample Grams Grains Gram h A
2
2
4
n
d
C
4
1
3
5 6 7
13 14
4
R
2
i
c
IF,
11:
0.148
0.146 0.206 0.208 0.21'5 0.286 0.222
C
?3%
I.Jv"Cr 1
From these results i t is apparent t h a t in general for such materials, t h e method is accurate t o 0.01 per cent vanadium. If chromium also is t o he determined, i t is determined in a separate portion of t h e sample, using a n y of t h e usual volumetric methods. AYERICAN STBBL~ O U N D R I K S . CIIICAGO
-____
THE EFFECT OF CERTAIN ORGANIC COMPOUNDS ON WHEAT PLANTS IN THE SOIL-PRELIMINARY PAPER BY Faso W. UPSONA N D A. R. POWBLL Received March 20. 1915
In recent years our knowledge of t h e chemical nature of soil organic matter has been greatly extended through t h e work of a number of investigators, chief among whom are Jodidi a n d t h e several workers in soil fertility investigations of t h e United States Bureau of Soils. A very complete historical account of t h e work on soil organic, m a t t e r a n d of t h e older views regarding i t has been presented by Schreiner a n d Shorey' a n d b y Jodidi.z Through t h e work of these 1
Bull. 63,Bur. oi Soils, U.S . Dept. Agr.. p. 21. Biockrm. Bull. 3, 17.
2
3 PL*TC
4
I
by thesc investigators on the toxic effect of organic compounds has bcen determined by growing plants for short periods i n distilled water culturcs containing t h e various compounds, The organic ,compounds studied are either those which have been isalat.ed f r o m t h e soil or those which may result through t h e breaking down of plant a n d animal residues. Many of t h e compounds studied have been shown t o be more or less toxic t o wheat plants in comparatively low concentrations, 1 0 - 2 0 0 parts per million of solution. Some few have heen found beneficial t o t h e growth of wheat plants in water solution. In many cases t h e addition of fertilizer salts t o t h e culture solution has partially or completely overcome t h e toxic effects of t h e organic compounds. While a knowledge of t h e effect of these compounds on t h e growth of wheat seedlings in water solution is of t h e greatcst importance, nevertheless we should I A Summary of the effect of varioun organic compounds en growth 1% given in Bull. 81, Bur. of Soils. U. S. Dept. A=.. p. 7 0 . 2 Sehieiner and Skinner have studied the effect of cumarin (Bull. 17, Bur. Soils, p. 16) and of ralieylic aldehyde, U. S. Depf. Agr. (Bull. 108, 5. IZ), an =heat Plants in the mil.
May, 191j
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
n o t assume from results obtained in t h i s manner t h a t these compounds will exhibit t h e same behavior t o ward plants growing i n t h e soil. Conditions are much more complex in t h e soil. Adsorption a n d other surface effects, aeration, t h e effect of chemical compounds a n d t h e action of microorganisms are all factors which are of little importance in t h e water culture, b u t which play a much more prominent r81e in :he soil. Extensive work on t h e behavior of these organic compounds toward plants in t h e soil. is necessary before we are able t o draly final conclusions i n regard t o t h e relation of these substances t o soil fertility. C X P E R I 31E 1-T A L P A R T
T h e present paper deals with t h e behavior of vanillin, salicylic aldehyde, cumarin, quinone a n d dihydroxystearic acid toward wheat plants in t h e soil. Vanillin is of special interest because i t exists in m a n y plants in t h e form of a glucoside. Vanillin or substances m-hich give rise t o it h a w been reported in oats,' asparagus shoots2 a n d other plants. Quite3 recently i t h a s been isolated from ungerminated 13-heat seeds a n d from seedlings five d a y s old. I t has recently also been isolated from Florida soils.4 \-anillin has been shown b y Schreiner. Reed a n d Skinner5 t o be toxic t o wheat seedlings g r o n n in distilled water solution, j o o p a r t s per million being sufficient t o cause death in nine days. I t was noticeably toxic in much lower concentrations. Schreiner a n d Skinner6 have shown also t h a t vanillin is much less toxic in water solution i n t h e presence of fertilizer salts. EXPERIMENT I-The soil used in this experiment came from a meadow whicli has long been in blue grass. It is a black silt loam of excellent texture and rich in organic matter. Approximately 1 8 0 0 g of dry soil were mixed with the required amounts of vanillin, potted and brought to the proper moisture content with distilled water After standing 24 hours, ten wheatseeds were planted in each pot. Complete germination was secured in each. After the plants were well sprouted each pot was thinned to five plants. The experiment lasted from October 2 0 to November 28th (39 days). At the end of this time the pots were opened, the soil very carefully removed from the roots and the green and dry weights of the whole plant determined. The results are shown in Table I, A . '
TABLEI-RESULTS
WITH
VANILLIN
A
C
B
r _ _ _ & _ _ L _
$
TREATMENT ....., . . . .. ,
. . 19.2 2.21 2 Same 250 p. p . m. vanillin 19.2 2.20 3 S a m e f 500 p . p . m . vanillin 18.8 2.09 4 Same I000 p . p. m. vanillin 18.6 2.16 1 Soil u n t r e a t e d . .
+ +
100 100 98 97
48.1 51.5 47.7 48.4
7.58 7.43 7.20 7.46
100 107 99 101
51.0 51.8 58.2 50.1
6.4 6.39 7.13 6.57
100 101 114 98
T h e roots were n o t visibly injured in a n y way even in t h e highest concentration of vanillin. A photograph serves t o show this more clearly. Plate I shows t h e plants from Experiment I : Nos. I , 2 , 3 a n d 4 show t h e plants from t h e untreated soil a n d from t h e soil de Rawton, Comfit. rend., 135, 797. von Lippman. Ber., 18, 1335. a Sullivan, THIS J O U R N A L , 6, 920. Shorey. J . Agr. Res., 1, 357. 6 Bur. Soils, U. S. Dept. Agr., Bull. 47, 31. 5 Ibid.. Bull. 7 7 , 20. 1
421
containing 2 jo, joo a n d 1000 p a r t s per million vanillin respectively. EXPERIMENT z-This is a duplicate of the first experiment except that the plants grew till December 23rd (64 days). The results are shown under B in Table I. EXPERIMENT 3-This experiment was carried out in the same manner as Experiments I a,nd 2 except that the vanillin was added to the soil in water solution. This experiment ran from October 30th t o December 29th (60 days). The results are given under C in Table I. EXPERIMEXT 4-Another experiment was carried out using soil from a field which has been under cultivation for about thirty years. It is a silt loam of excellent texture, but much less fertile than the soil used in the previous experiments. The plants grew from November 30th to February 3rd. Three plants were grown in each pot, the green weights of the tops only being recorded (Table 11). TABLE
II-RESCLTS
WITH V A N I L L I S
Re!Green Relative Green ative TREATXEST No. weight growth No. weight growth S o i l u n t r e a t e d . . _ . . . . . _ ._. .. . . .. . I 100 100 4 6.69 6.5 Same 500 p , p. m. vanillin.. . . 2 6.39 9, 5 6.59 99 Same 1000 p. p. m. vanillin . . . . 3 5.9 90 6 6.49 97
+ +
These experiments show t h a t vanillin is not appreciably toxic t o wheat plants when present in t h e soil el-en in quantities as high as 1000 p a r t s per million. \-anillin is therefore, t o s a y t h e least, much less toxic in t h e soil t h a n i n mater cultures. Evcn with t h e addition of fertilizer salts in t h e most favorable combinations. solutions containing only j o parts per million of vanillin gave a relative growth of wheat plants' of 8s. Salicylic aldehyde has very recently been found i n a soil b y Schreiner a n d Skinner.2 These investigators have also determined i t s effect on corn a n d wheat in distilled water cultures a n d also in t h e soil. T h e y find t h a t in distilled water, growth of wheat is reduced by t h e presence of 2 j p a r t s per million salicylic aldehyde, 69 per cent a n d t h a t in concentrations of j o , I O O a n d zoo p a r t s per million this substance produced death.3 X u c h t h e same effect was produced on corn grown in nutrient solutions: I O p a r t s per million of t h e aldehyde gave a relative growth of 6 0 after 25 days, whereas zoo p a r t s per million gave a relative growth of only IO. T h e effect of salicylic aldehyde on 1%-heata n d corn i n soil in p o t s mas also determined.4 Salicylic aldehyde in j o p a r t s per million gave a relative growth of wheat of 61, after 2 2 d a y s a n d in concentrations of I O O a n d zoo p a r t s per million caused death: j o parts per million of t h e aldehyde reduced t h e growth of corn in soil 2 4 per cent a n d i n q u a r t z sand 60 per cent. These experiments were carried o u t i n paraffined Tire pots described in Circular 18 of t h e Bureau of Soils. E X P E R I M E N T S W I T H SALICYLIC ALDEHYDE
F o r these experiments t h e soil selected was t h e same as t h e one used i n Experiment 4 with vanillin. P o t s holding a b o u t 1800 g. of soil were employed. T h e aldehyde was dissolved in water a n d added t o t h e soil i n t h e proper proportions. Schreiner a n d Skinner, Bur. Soils, U. S. Dept. Agr., Bull. 7 7 , 21. U. S. Dept. Agr., Bull. 108, 1 (1914). a I b i d . , 108, 3; Skinner, Biochem. Bull. 3, 390; J . A m . SOC.Agron., 6, 1
108. 4
U. S. D e p t . Agr., Bull. 108, 5.
T H E J O L - R N A L O F I N D C S T R I A L A N D ELVGILVEERIiVG C H E M I S T R Y
422
EXPERIMENT 5-This experiment with salicylic aldehyde was carried out in the same manner as the vanillin experiments. Ten wheat seeds were planted in each pot and the plants thinned t o five after they were well sprouted. The experiment ran from November zznd t o January 2nd. Section -4 of Table I11 shows t h e weights of the tops only.
TABLE 111-RESULTS
WITH
B
NO.
1 2 3 4 5
Soil u n t r e a t e d . . . . . . . . . . . . . . . . . . . . . . . Same 10 p . p . m. salicylic aldehyde Same 25 p . p . m. salicylic aldehyde Same f 50 p. p . m. salicylic aldehyde Same f 100 p. p . m. salicylic aldehyde
+ +
EXPERIMENT
6-This
6.7 6.8 6.2 5.7 6.2
.85 100 1 2 . 7 .89 102 1 2 . 1 , 7 7 93 1 1 . 8 . 7 3 8.5 12.2 .75 93 1 2 . 3
2 . 5 1 100 2 . 2 9 95 2 . 3 0 93 2 . 4 2 96 2 . 4 7 97
experiment is a duplicate of Experiment The results are shown
5, except that it ran till January 28th. under B in Table 111.
EXPERIMENT 7-The same method was used as in the preceding experiments, except that higher concentrations of the aldehyde were used and the experiment ran from January I jth t o March 6th. A of Table IV gives the results.
TABLE IV-RESULTS
WITH
SALICYLIC ALDEHYDE A
j
plants in t h e soil indicate t h a t t h e effect is entirely different from t h e effect of these substances i n water solutions. Quinone in concentrations below 500 p a r t s per million in soil is beneficial t o t h e growth of wheat. T h e other t w o substances are somewhat more toxic i n t h e soil t h a n is vanillin. A complete series of experiments with these compounds is i n progress. Experiments are also in progress t o determine t h e f a t e of these tompounds a n d also of vanillin a n d salicylic aldehyde, i n t h e soil.
SALICYLIC ALDEHYDE A
v01. 7 , NO.
C 0 N C L US I 0 S S '
T h e behavior of vanillin a n d of salicylic aldehyde toward wheat plants in t h e soil is shown t o be quite different from t h e behavior of these substances in water cultures. T h e behavior of salicylic aldehyde is shown t o be different in different soils. T h e necessity for more extended experiments of t h e nature of those here reported, has been demonstrated. LABORATORY OF AGRICULTURAL CHEMISTRY UNIVERSITYOF NEBRASKA EXPERIMENT STATION
LINCOLN
B
I---
THE ENGINEERING PROPERTIES OF SOILS By R. 0. E. D A V I S ~ Received February 6, 1915
Treatment
IiO.
1 Soil u n t r e a t e d . . . . . . . . . . . . . . . . . . . . . . . 2 Same 100 p. p . m. salicylic aldehyde 3 Same 200 p . p . m . salicylic aldehyde 4 Same 500 p . p. m. salicylic aldehyde
+ + +
8.5 7.8 8.4 8.0
1 . 6 100 4 . 5 1 . 5 5 92 3 , 8 1 . 7 3 99 3 . 3 1 . 5 9 94 4 . 4
. 3 3 100 .25 84 . 2 0 73 .34 98
T h e engineering properties of soils are of interest t o all peoples living under civilized conditions, a n d engineering questions concerning t h e soil are of imEXPERIMENT 8-The effect of salicylic aldehyde on corn was also determined. The experiment ran from February 3rd to portance next t o t h a t of productiveness. T h e conMarch 6th. Two plants were grown in each pot and the method struction a n d maintenance of drainage, irrigation o r was the same as the one used in the wheat experiments. The commercial canals, t h e proper foundations for archiresults are given under B in Table IV. tectural structures, t h e construction a n d operation Our experiments indicate t h a t salicylic aldehyde is with safety of mines a n d quarries, a n d t h e protection much less toxic t o wheat a n d corn plants in t h e soil afforded b y levees a n d embankments are all dependent t h a n in water cultures. T h e toxic effect on %-heat, directly in most cases a n d indirectly always on these e v e n i n a concentration of joo p a r t s per million, is engineering properties. Attention has n o t been given practically negligible. This does not agree with t h e t o t h e subject in proportion t o i t s importance. Lately, results of Schreiner a n d Skinner.' I n order t o de- however, engineers a n d engineering societies have termine whether this difference was due t o t h e method evidenced a growing interest in t h e subject, as i t is or t o t h e soil we repeated t h e experiment, using t h e realized t h a t while t h e engineering features of t h e paraffine wire pots according t o t h e method of Schreiner superstructures have been worked o u t with much care a n d detail, t h e properties of t h e soil on which t h e a n d Skinner.' foundation rests are very little understood. EXPERIMENT 9-Wheat was grown for twenty-two days in T h e statement has been made t h a t nothing is known paraffined pots. At the end of this time the tops only of the six plants from the check pot weighed 0.98 g. while those from the of these properties. This, however, is rather misp o t treated with IOO parts per million of the aldehyde weighed leading; t h e facts are t h a t t h e properties t h a t t h e engi1.09 g. The soil which we used was a silt loam of loose texture neer has t o deal with are mainly t h e physical properties and fairly high in organic matter, while the one used by Schreiner of t h e soil a n d these have been studied systematically and Skinner is described as "a heavy clay loam." f o r some years, mainly from t h e agricultural s t a n d Our experiments show t h a t t h e effect of salicylic point. So i t is well t o see i n w h a t way t h e t w o studies aldehyde on t h e growth of wheat a n d corn is different are related so t h a t needless work m a y be avoided. f o r different soils. We are of t h e opinion t h a t aeration Approaching t h e problem from t h e engineering a n d absorption are i m p o r t a n t factors in overcoming standpoint, t h e properties of t h e soil on which t h e t h e effect of t h e aldehyde. It is probable t h a t t h e engineer wishes information are t h e rigidity of the explanation of our results is t o be found i n t h e fact soil, i t s cohesiveness, i t s penetrability, a n d i t s porosity. t h a t t h e soil used was of a looser texture a n d more These are t h e properties t h a t determihe t h e weight absorptive t h a n t h e one described b y Schreiner a n d which t h e soil will support under structural condiSkinner. tions, t h e height t o which a retaining wall of soil will Preliminary experiments on t h e behavior of cumarin, s t a n d without additional support, t h e resistance quinone a n d dihydroxystearic acid toward wheat 1 Scientist in Soil Laboratory Investigations, Bureau of Soils, U. S. 1 LOC.
Cil.
Dept. of Agriculture.
