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0-169

 

This is to certify that the

thesis entitled

The Effect of Calcium Carbonate on the
Manganese status of Five Acid Organic Soils

presented by

John C. Shickluna

has been accepted towards fulfillment
of the requirements for

Master OLSQEnQLdegree in_S.QiLS.cience

Major professor

Date AuguSt 233 1951

 

 

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Cit: EU

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John C.
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h ‘aAJ—JS-LD

Submitted to the School of Grecuete
State College of Qtricultur e and

in partial fuli'illment of the

for the degree of

\l-I‘F‘] ‘1-r1-~

LJ'LLJL rm (IF

('11 IT?

‘— ALA—J

E FIVE ACID CESAR

Shickluna

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7 .“7f‘ .1 vficxrw
lcnx-‘e‘! \‘Y-_Lo‘;U;-l

IC oC‘LS

Studies of ric.1
Applied Science
re :ysil e1 1e.'1ts

€111

Depertrent of Soil Science

195

(HESIS

ACKNOJLEDGSKEAT

The author expresses his sincere appreciation to
Dr. J. F. Davis for his helpful suggestions and guidance
throughout the progress of the work. The writer is

/‘

tirk Lawton and Dr. E. J. Benne for their

H

indebted to Dr.
hind assistance and advice and to Dr. L. H. Turk for his
guidance during the course of study and for his criticism
of the manuscript.

He eccnowledges the helpful sufljestions given to

U v.0}

him by his fellow graduate students.

IlJTRODUC TIOII o

REVIEJ Or LITERATURE

PROCEDURE . .

BETHCDS OF CdEEICAL ANALYSIS
EXPERILELTAL RESULTS

DISCUSSION . .
SU—hfi HAL-I. o o o

BILLIOGRAPn“I .

TABLE OF COI

Page

ll
14

47
55
59

’ m I all
IJlRQDUCTICn

The in:01tence of an ade nus te supply of calcium in
rganic soils has lone been reco; nized as essential for
'ields. Lowever, specific informativn regard-
ing rates of epolicetion of calcium reguired to bring about
Optimum conditions in acid organic soils is limited.

It is imoortant to recognize not only the beneficial

5

effects of cm cium, we li ed in the form of lime (calcium
carbonate) in Optimum amounts but also gossible detrimental
effects associated with overliming.

Soil reaction (pH) is gene ally considered as a
pre cticel measure oi the lime neeis oi an organic soil.
It has been observed, however, that creps growing on organic
soils with similar soil reaction vary in the degree of

eSponse irom lin e aoultcationt. In extreme cases fair

crops of onions have been piodiced on soils with a l w pH
and on other organic soils with the same p3 a crop failure
would r Silt. Soil reaction, therefore, does not appear in
all cases, to be the only criterion by which the lime require-
ment of an organic soil 0&1 be base

Wnile tne need for line is re00311ized as a recommended
soil mare er“nt practice, the addition of excessive amounts

of lime to a soil SM1 uld Le avoide d in order to grevent tne

inducing of certain micro-nutrient ml n1ent delician~s,

notably manganese. manganese, iron and aluminum availabilities
are highest in the soil reaction range from intensely acid
(pH 5.0 - 5.9) to strongly acid (pi 4.6 to 5.1).

It is imoortant that these micro-nutrient elements are

in Optinum amounts in the soil, thus preventing a deficiency

U)
(I)

' 71 .2: .
‘J

when too little is present or a toxicity when they are oi vrt

d
O
O

in excess. The former condition commonly occurs on soils

heavily limed, Whereas the latter condition freguently arises
when the soils are too acid and in need of lime.

The followine studv was instituted to investi ate a
b v C:

umber of factors that might be associated with the causes

0? variation in the response of different acid organic soils

.5.

to lime agplications.

-3-

'

BEVIiJ CF LITEnnTUKB

L4
,4
H
L.)
0.1
Lv.
j
‘1
*2!
C)
( f)
I I
x ‘ .

,. 1,. . , .1-'.-. ' - ”131° '1 -__‘1
acts t1e L"D§er‘lcS o1 szhulc soils nave

la (37).

1.1.

bee n resorted to be similar to tntse oi mineral so
Organic soils tossess, as do mineral soils, the prooerty of
ionic exchin;e (19, 24). The difference is one or degree,

peat soils containing more aosorbed cations than do mineral

15 inb1eren differences were

tl.

found between tdese soi s. Beat soils, contai1ing compara-
‘ ceflgxhnn were 0: e111011<iist11ctl

acid in characts” (33), diffe1i1: in this resoe ct Iron

soils.

Nilson and Staker (57), investigatin the ionic eX1an.e
of peat scils found hat organic soils ‘iffered quite widely

‘le hydr0¢en, had a high absorptive
1acitv for cations and to contain large amounts of “eglaceaele
cations in congarison with the a1ounts usually found in mineral
soils. An inverse correlation was observed between the degree

of acic ity a11 r

(D

1leceable catiins. Little relationsnip
between the tot; 1 ex 1161158 catacity and 1-3.1 was iound to exis
and e::x:u11;e ca;ecity :as rnnzxmacessarily azihtnstion of the
:Xi (1.).

1

riulrily to bring ctlcium into the clay humus fraction of

-4-
the soil (lime absorption) a1d theieb37 increase the amount of
alci um oer 100 parts of humus and the de5ree of case saturation.

L

5_ structure and soil reaction also

._J
(0
O
(.1
_J

beneficial changes i“

D

resulted. Line not adsorbed either remained in the carbonate
fort or was regidly transformed into this form.
hiss1nk (lo) workin5 with lime additions on or5anic

1

oils found {1 relationshio betw e11 the three values: pm, the

(0

"I

de5ree 01 satu1ation of t1e base exc1an5 e corn Jex and
milligramequivalents of bases present.

Jilson and Sta“er (37) and Gedroiz (l0) have gointed
out that calcium is the predominant exchan5eable cation on
the base exc1%1 a com ‘Ml X.

Ge1roiz (10) 1e p01 ted t.n t the order of relative ma5 ni-
tude of the proeortions in which cations occur in most soils
is Ca, K5, K and Na, accordin5 to the decree sir15 ener5y of
aosorption. It has been shown (5, 7, 25) that an excessive
concentration 01 calcium i015 tends to decrease the absorption
of other nutrient ions

Moser 25) studyi15 the calcium nutrition of plants at
vaiious oH levels oelO1 neut1ality found 5ood correlation of
plant growth with calcium concentra tio:. With three types
of ulants, sorbeans, lesseieza and sor5hum, it was found
the pH was a minor factor in comgarison to the suoply of

available calcium. Incr1asin5 the su ply of available calcium

.3-

resulted in increases in plant growth and the absorption of
the other nutrient elements.

Davis and Brewer (5) pointed out that comgaratively
large quantities of calcium are essential to glant growth.
They found that normal absorption of other ions aepe nded on
a certain minimal 1uantity of calcium ions, the amount vary-
ing with the plant studied.

Harmer (l4) stated tth the annual harvesting of good
yields of crops from muck L nd resulted in the gradual removal
of cc Lr“rxeratle LLKXMICS of lira; Mll'tle for: of ml iina and
meanes:Lum compounds in those crOps. If the muck was well
supglied with lime, this removal had little or no effect on
the on or the productivity of the soil. lost crops will grow
mortali; ~.ith piooe fertilization with the muck soil reaction
down as low as 4.6. however, he stated the range in adaptable
muck soil reaction for onions was between 5.0 and 6.6.

Davis (4) has used lime at the ratio or 4 to lo tons
per acre to correct extreme conditions of acidity. He stated
that the amount used depended upon the acidity and type of
conszioei ed a pn of 5.0 to 6.0 as ideal for most

crogs that woqld be grown on muck soils, with the exception

{D

01 cranberries and clubberiioo. He “so iouid t1at the pl
of the muck is in part correlated with micro-nutrient element

HGEQSo

-5-
Pierre $11 Allaway (25 mentioned that a decrease in
solubility of manganese and iron may occur as the hydrogen
ion concentration of the soil decreases, but it is difficult
to distinguish between an unavailable form resulting from
reaction a11d inability of the plant to utilize them as a

'1

result 0: excess calcium in the pl ant. Piper (27) has shown
that the solubility of manganese is intimately controlled by
the soil reaction and by the oxidation-reduction equilibrium.

8&1 rman and Earner (oi)b ave shown that neutral and
alkaline conditions favor the formation oi ma5a1ic manganese
and acid conditions of mzfl1 anous man5anese. Strong reducing
a5ents are capable of reversing the oxidative equilibrium.
In general, as the nan5anous ion decreases in the soil, the
easily reducible KnOQ increases and, as the “a 5anous ion
increases, KnOg decreases. They have stated that in alkaline
soils at least 3 p.p.m. of exchangeable manganese must be
present for satis iactory crop production. In order to main—
tain an adequate level of the exchan5eable fraction this must
be supplemented by at least 103 p.p.m. of easily reducible
11131115: a :11? S e o

Kann (18) studied the effect of additions of calcium
and mangesium ca1bo1ates on the water solubility of manganese
in two acid soils. He found that the solubility of manganese

was rapidly decreased by both carbonates as the soil reaction

-7-

became less acid and only a trace of water soluble mansanese

5.4

'T

was detected at pd 7.0. :e also found that increasing
dressings of the carbonates of calcium and ma5nesium steadily
decreased the amount of man5anese in the crop until near
neutrality the plant exhibited typical symptoms of man5anese
deficiency.

Lynd and Turk (17) found that lime proved highly
beneficial to crOp growth, but definite injury occurred
when the lime requirement of the soil was exceeded. They
found that a marked decrease in exchan5eable manganese in
the soil resulted from increased rates of lime.

Funchess (9) observed that applications of lime to
acid soils decreased the amount of replaceable man5anese.
The lime-induced chlorosis reported by Gilbert, thean and
Hardin (ll) was accompanied by a low manganese content of
plants growing on limed soils, as compared with those
growing on more acid soils. Harmer (14) stated, however,

3 V ‘ V

that althou5h it is true that those mucas wnico show a need
for manganese generally have a fairly high pH, occasionally
alkaline mucks do not require manganese. Russell (52)

stated that soils on which manganese deficiency exists are

generally reclaimed peats rich in orga1ic matter and made

alkaline by lime.

-3-

Davis (4) found when the pH of the soil reacued 6.5 or
above, mani1ne e in the form of manxcnese sulfate, was required
by a number of crOps, such as onions, celery, Spearmint,
lettuce, table beets, potatoes, carrots, peas, beans, sudan
grass and oats.

The work of Prince and Toth (50) revealed that exchange-
able manganese decreased with increasing lime application and
on. The: bas ed this difference in exchangeable manganese due
to the exchange between the adsorbed man awne e and calcium
ions in the solution. The result is a precipitation of the
forner cation as insoluble man: an ese hydroxide which may be
oxidized to MnOg.

kchargue (20) reported that manganese in the slant is
connected with carbon assimilation, and in this resgect the
higher concentration of nan anes e in the leav and the lower
concentrations in the roots of various slants is interesting.
Remington and shiver (31), in examining a number of different
vege ables found from three to eight times as much manganese
in the leafy parts as in the roots.

The availability of mansr105c and iron are affected
in much the same manner, but as sho own by the work of Willis
and Carrero (39 the solubility of iron and the amount avail-
able to plants cannot be ta“en as a certain determinant of

the efficiency of iron.

-9-
Hahn (l8) working with soyleans grown on heavily
limed soils also concluded that the solubility of iron and

-.

manga‘we e in soils the iron and manganese contained in

1

plants and the chlorotic plants that resulted is not
associated with a deficiency f iron, but is Specifically
due to a deficiency of manganese.

Although apparently not as common an occurrence as

W

aluminum toxicity, manganese toxicity nas been reported by
a number of investigators. Jacobson and Swanback (16)
state‘ that a definite correlation was established between
reaction of the soil and manganese content of the plant
materia s, viz., the higher the acidity, the greater the
yercentage of manganese found in the plant mater rial, until
a toxic amount resulted. Blair and Prince (1) found with
slight exception, the manganese content of the crOp decreased
as the amount of lime aoplied to the soil inCiWea ed. Emmert
(5 ) increased the manganese content of lettuce by adding
sulfuric acid to the soil and obtained a chlorosis and
reduced growth which be attributed to mangan se toxicity.
The occurrence of soluble man anese in an acid soil may be
one of the causes of toxicity in such soils as exhibit toxic
effects according to Echargue (El).

Ha reel (14) has also shown that the addition of sulfur

to alkaline nuchs is oxidized to form sulfuric acid in the

-lC-

soil which permem nently lowers the pH an d increases the avail-
ability of the phosyhate, man;anese and boron corgounds

pressznt in an unavailable condition in the alkaline muck.

Host of the evidence as to what causes the injurious

(0

effects of acid soil on glants supports the View that it i

88 €110 .111

(1"

due to toxic amoints of soluble aluminum or angsn
some cases to a combined ef‘
he .'ever, aluminum has been found to be the toxic principle
(22, 2.9).

Grist (3) found that a,olicetions of lime area ly
reduced the intake of iron and a uminum by the plant.
Hardenburg (15) reported that there is some indication that
the iron and aluminum in lettuce tissue decreasad Iith
increasing pH values of the soil.

Truog (36) concluued the main harmful influence of
soil acidity on certain plants is due to its influence in

nlants from getting, at a suffic1ently

.L‘

preventing these

he albeiete or bi-carbonate.

-.

rapid rate, the calcium as t
Calcium is n>e ed to neutrali and precipitate certain

acids in the plants th rselves, which ale grobsbly largely

(7)

by-products, produced as a sult of certain vital lee ctions

. Ii calcium in these forms is

(O

in the growth of the plant

{I I.

not furnished at a SUlll iently rapid rate, then the rate of

0

these reactions is lowered CCOiQLb-'v as is also the rate

of plant growth.

iect of the two. In most instances

Five acid organic soils were obtained from the
following locations in Lichigsn during October and November,
1350, from the unper 3 inches of the soil profile.

Soil hunter 1 Trebish Farm, Livingston County

2 - Anderson Farm, Lapee" County
3 - Vicinity of Capitol Airport, Ingham County
4 - Schoenfeld Farm, napeer County
5 - fiorton Farm, Clinton County
The soils were dried to an apparent Optimum moisture
content and each soil was sieved through a 1/4 inch screen.
The soil was unifornly mixed and a ten-gram samgle of each
soil was dried over night at 1150 C. tocietermine the
moisture content.
Determinations of pH were made on duplicate sangles
at the previously determined moisture percentages by the

glass electrode method.

Lime was added to the soil in two-ton increments
resulting in soil treatments varying from S to 12 tons per
acre. Each treatment was reglicated three times. in
unlined treatment was included in each case.

A basic treatment of 2000 pounds of 5-9-18 fertilizer
and 100 pounds of c0pper sulfate per acre was added to all

the treatments of the five soils.

-13-

The ad dition of c0p 9 er to organic soils with a pH of
6.5 or lov.e er is very imROLtant for Faxirim crOp production
of a number crOps. Besides resultin5 in increased yields to
many crops, it has been reycrted to improve the color and
quality of onions, cazrots, lettuce and spinach (14).

The soil, lime, iertilizer and c0pger sulfate were
thorou5hly mixed and placed in one gallon jars.

On January 19, 1951, the jars were seeded 5/4 to
1 inch deep with Erigham's Yellow Globe, a medium matU'in
variety of onions.

Prior to seeding, the seeds were treated with "Arasan"
to prevent damage from soil borne organisms.

The onions in each pot Jere thinned to four onions

The soils were main ained at optimum moisture conditions
by ueriodically b1715in2 the jars up to weight with distilled
water. Notes were recorded and i}hOtOg; rephs taken of the
plants to show the difierences that develok‘ ed.

The onions were harvested on June 21, 1951. Air dry
weights of the toys and bulbs were recorded.

The untreated soils were chemically analyzed for the
following constituents: Exchangeable calcium, mag 5nesium,
potassium, sodium, man5anese and iron, and total iron,

aluminum and man5J ane se. In addition the following Jroperties

-13-
were determined: pd, exchangeable hydrogen, total exchan5e
capacity, exchan5eable cations (total bases) and per cent
base saturation.

The lime requirement for each soil was determined.

Exchangeable and easily reducible manganese and pH
were determined on the soils "fter treatment with calcium
carbonate and following the harvestin5 of the onions.

Total manganese determinations were made on oven-
dried tissue from the tOps and the bulbs of the onions to
investigate the relationship of the amount of man5anese
present in the plants and the amount available to the plants

at the various soil reactions obtained after limin5; and to

see what effect, if any, this had on the growth and yield

-14-

KLTHCDS OF CHEEICAL ANALYSIS

Ease Exchange Capacity5Determiiation (55)

Place 5 grars of air dry soil in a 300 ml. flash and
add 250 ml. of ieutre. N ammonium acetate solution. Shake
at intervals from 1/2 hour to 1 hour, and then pour into a
funnel fitted with a number 48 filter paper. Allow to
drain; then leach with an additional 100 m1. of 0.1 N
ammonium acetate. After the soil in the funnel has finished
draining leach the soil slowly with 200 ml. of 10 per cent
NaCl.

Place the salt filtrate in a Kjeldahl flash, add
20 ml. of 2 N NaOH and distill into 50 ml. of 4 per cent
boric acid solution. Titrate distillate with 0.1 N HCl
using brome cresol green as the indicator.

Note: After the soil has been leached with 0.1 N
ammonium acetate solution, it must be washed with an in-
definite amount of distilled water and 85 to 90 per cent
ethyl alcohol until all the occluded ammonia has been
removed. To check for absence of ammonia add 1 drOp of
Nessler's reagent to 3 drOps of the leachate. Compare the
color obtained against a color chart for ammonia. A very
pale yellow color indicates approximately 1 par per million

of ammonia present.

Determi: atiozx of Total Eases (a)

Extract the soil by the 5 me procedure used in the
determination of the base exc‘11ance cs pacitV.

Collect the filtrate and evaporate to dryness on a
hot plate. Transfer the residue to a orcelain ev boretihb
dish and gently ignite over a meeker burner for a few minutes
and then at full red heat for 10 minutes. After cooling,
add a calculated excess of 0.2 N HCl, warm the solution and
rub the bottom of the dish with a rubber ooliceman. Add
5 drone of m tllyl red indicator. The solution should be red.
Back titrate with 0.1 N HaCH. Calculate the milliequivalents

of soil b.ses per 100 g'ams of soil.

CO

{Tl

Per cent ese Ca ture ion

 

From the base exchange cagacity and total has
determinations the per cent base 9 t iration may be deter: lined
in the following manner:

e1 bases
Exchan; e Capacity x 100 = per cent base saturation

 

:5

h’ -
(D

Excnangeaole Liyd; cten

 

Fro m the base exchange capacity and the total base
determinations of a soil, the exchangeable hydrogen may be

calcm11 ted in the following manner:

Ease Exchange Cagacity - total bases = Exchaigeable

hydrogen

-15-

The_Dete rmination of Calcium, Sodium and Potassiumgby the

 

Flame Photome ter (35)

 

f

Preparation of Solution A

Extract the soil by the same procedure used in the
determination of the base exchange capacity.

Collect the filtrate and evaporate nearl 3 to dryness.
Pour into alCO ml. volumetric flasr. Cool, dilute to
100ml. and label as solution A.

Pipette 50 ml. of solution A into a lOC ml. volumetric
flask, add 10 ml. of 250 p.b.m. lithium chloride solution,
and dilute to 100 ml. The solution is now ready for he
determination of calcium, sodium and potassium.

Calcium

Warm up the flame photometer using the blue photocell
for at lea st one-h alf hour grior to its use. Locate the
position of the calcium line on the wave length scale with
a solution containing 60 p.p.m. calcium in the form of

aClB.2HgC. With the location established, reset the
nac1ine for the indirect method of determin atic,r', using
85 p.p.m. lithium in the form of the chloride as the internal
standard. Set the 60 p.p.m. calcium solution containii'
25 9.9.m. lithium at 100 and chec one 3 int on the curve
to be sure that the machine is working saois f- actorily.

A

A 30 p.p.m. calcium solution should read 50 scale divisions

-17-
when the 60 p.p.m. calc iurJ solution is set at 100. Pour
unknowns in the funnel of the flame photometer and record
scale readings.

30 Cl um

5

Locate the position of the s ooium line on th wa—ve

(D

length scale using a solution containing 20 p.p.r. sodium

in the form of sodium chloride. with the location established

set the machine for the indirect method of determination
using 25 p.p.m. lithium as the internal standard. Set the
CO p.g.m. sou ium solution containing 25 g.p.m. lithium at

100, and c‘;1ec one ,oint on the curve. A lO-p.p.m. sodium

scale divisions when the SO p.p.m.

.._1
U)
[.3
O
f.
C;
'7'
{.3
r4
(‘1
‘ D

solutioi
sodium solution is set at 100. Pour unknowns into the

C.‘
u.

funnel of the flame photometer and record scale read'n:

Read p.p.m. Sodium from curve.
71.. '
:o aSSium

Remove the blue ghotocell from the photometer and

1 W I.

alace with thx: red giot oceil. Loo; te the JOSitiOH oi the

l
‘ - J.

. ”x ‘ .. e 1,_.,..3..'..‘. “1A ..' ‘. “1.4.:
gotas sium 111: on tie N&Vu luaubfl scale Lita a solxtion of

,_.

n ’ V‘ firm a 4 '. “ A ' n 1 ,-~ (- “.fi! 4 1‘. '0. ‘
6o o.o.m. outassium in the form oi thdSSl’U cnlOLioe.

With the locatf establis hed reset the instrument for

t.
O
,.'

1 - ',-,“ '-,.~ -,.-. 1..“ u ‘.\4. , .. .' , - .f . . n", .. -.
tile: Ahlli‘dct lbdtlou OJ. (1*; bel111£-LilC.t.LOll, \.1S.gllo (L); 1",. 3.17..

lithium in the form of the chloride as the internal standard.

Set the cG—3. .p.m. potassium solution containing 23 y.f.m.

-13-
lithium at 10C, and check one point on the curve. A 50~p.o.m.
potassium solution read a' scale divisions when the 60-p.9.m.
K solution '8 set at 1C0. Pour unknowns into the funnel of
the flame photometer and record scale reading

GPA r) "..‘.T‘..
‘ db.“ L . ‘5.» a“

from the standard curve.

Determination of 1:;neoium (E )

 

(D

In this method for the determination of ma tn sium,

it "as found that a lO ml. aliau1ot of the samole and lO

0
0
Fa
v—J
(D
('l
t

(1'
*3
o
(”f
P
O
k .1
H
0
Ft

of sodium hydroxide Wi.th a 200 grams per
lite r, proved best ior Lagn esium determinations on the
org"ic soils used in this study.

Since these soils are not garticu arly high in
magnesium, a smaller a iuot than 10 ml. did not contain
sufficient magnesium to get an accxrate test with Thiezol
Yellow. 10 ml. of sodium hydroxide with a conceimt': ti on
of 800 crane per litre was also required rather than a
concentration of 100 grams oer litre in order that the
required volume could be maintained and tin t the color
could be developed.

The procedure outlined by Drosdoff and hearpass (6)

was followed with the above modifications.

Weigh a 2-5 -ram sen 1e into an ignition crucible.
Ignite over night at ECO to 6000 C. Add 3-5 cc. of

1..

to the ash ani boil for 1 minute. Add

(D
'1

about 1" ml. of 1-vate: and filter. Lash “xvi h hot not
until it is free from nitrates (tcs filtrate with
diphenylamine).

Evaporate the filt‘ate to a volume of 10- 40 cc.,

them add l cc. 1305, 10 dro )5 of H3;O4 an 2-5 drogs of

H530; (helos t1e color to develoo faster), and 1 cc. of
periodic acid solution (30 5*ams per 130 cc. of water).

neat until tle iull color devol o os, then transier

to a volumetric f ask and leJ5 11 to voli (usually 1C"l cc.).
Read the tor cent trancu135ion 14 a photolomece“ or )1oto-

electric colorimeter, using filters 401 and 39: in combi-
nation for the inotolon ter and for tne ohotoelectric

co‘OIiI-ter a filter 01 too mu (millimicrvns ) wave leng th

fo: color combarison.

7" . .. ‘_ .. '1
F4 if mm, C '11 _‘\“ (“a .' C l to) I r~ ,1 w- (T .. (-3 Q ,3 . . fl
HJL‘J $(Al ;.-- ‘,._,, _, L--(_-'..L.}(_,_1..~., six, '4

 

Add 250 m1. of neutral nor mal um.oo1um acetate
solution to flask contai1ning the soil. Shake frequently
and filter. deturn so._l to ori inal flask for extraction
with ammonium acetate-hydroquinone solution. Evagorate

the filtrate to dryness and ignite over an open flame

-on-
Dissolve the residue in dilute H303 and determine an,1ncsc

by the 16110 date met1od.

Essilv- Reducible Ianganese Dioxide (34)

Add 250 ml. of ne utro normal ammonium acetate
solutio on containing 0.253 hydTOQUiHOflfi to flash containing
soil from which e1c1a12eaol1 .nng1ese has been remove'

(:11 1»- 1
111-11411: 001113;;

ts of flJa<sl;s frequerdflgfenmi filtei'i411fi1e same

te111ns ion of exchen eable manganese.

(T)

‘4» ,3
tLlL‘j U

H

'3
- . 1 \f’ 1 " ‘
I'L'cJini as .L O

(U

Lid 10 ml. (1-1) of HQCO4E m1i l0 to 20 ml. of concen rat d
EROS to filtrate and evaporate to dryness b

vigorouslv. The 3105 must be in excess so that, when liquid
agproacnes Frrness, it will foam, due to escaping nitrogen

ttering. It i essential that

(.1)

onldes and thus grevsnt s

6*

all hydquuinone be destroyed. Residue after evagoration
should he a t1enslucent mass. Dissolve residue in 25 to
50 ml. (1-4) of thC; and de to rmine man anese as previously

described.

 

‘1

Iron is deter11111ed co1orirxtr1cally as tn cierrcis
ortho-phenanthroline comglex. For tne determfnation of

exc 11111 :e atl e iron the soil is extracted with the ::e

\4

f D
o

amount and cmcentrstior oi" {11311TLOllilli'n acetate tT1a7.1za.s been

previous 1y described, and evaporated nearly to dryness on

a hot plate. Nash into a 25 ml. volumetric flask, add 0.5 ml.
5 per cent solution of byuroxylamine hydrocnloride and 1 ml.
0.20 oer cent solution ortho-phenanthroline in 25 per cent
alcohol. Lix and ad* a 60 per cent ammonium acetate solution
to obtain comrlete color develooment. Dilute to volume.
Prepare a set or standards simultaneously and read on a
photoelectric cclorimeter, using a filter of 530 mu wave
length for color com>arison. The color should be read

within 1 hour after its develogmcnt.

T tal Iron and Aluminum (26)

 

Ignite a 2-5 gram samgle ia an ignition crucible at
500-6000 C. over night.

Dissolve asn in 3-5 cc. of HHOs and dilute to a
volume of 250 cc. If the extract is known to be low in
phosyhorus add about 0.5 gram of (N14)2 HP04 before making
the dilution.

Add a few drops of thymol blue and then NH4OH until
the solution just turns yellow. Run in 0.5 ml. of concentrated
HO and follow with 25 m . of 25; ammonium acetate solution
and stir. Let stard at room temgerature until precipitate
settles (about 1 hour). Filter and wash 10 times :itb not
05 solution. Ignite and weigh as iron and

aluminum phOSphate.

QC“-

Pipette a 50 ml. aliquot from the original 25' ml.
into a 200 ml. beaker and evaporate to a volume of approxi-
mately 20 ml. Oxidize the ir n by adding KLn04 (l +' 1030
until a very faint permanganate color persists. Add 5 ml.
of 10 per cent 334CK3 solution and titrate With dilute
iClg solution to dis a )pe rance of red color. This Will
“ ive the amount of iron present.

Convert this amount of iron to FeP04 and subtract it
from the total amount of FePOl and AlP04 obtained on ibnition,
precipitation and wei nin;; this will give the amount of

anO4 present. both iron and aluminum phos ate C‘q be

converted to per cent iron and aluminum by Specified factors.

Edge Requirement Determination (41)

A buffered solution of the following composition was
P

prepared: are nitrophenol, 8 grams; calcium acetate

40 grams; and sodium hydroxide, 1.2 g'ams. The mixture

.as made up to 1 liter With distilled water. The pd of the
resulting solution was then adjusted to 7 at 250 C. With a
few drogs of dilute 301 or pellets of NaOH as required.

T‘JEWIt’ cubic centimeter of the buffered solution

U)

to a measured 2 gra.

a

were adde

:3

samgle of 40 me sh air- dried
soil in a 50 cc. g ass beaker. The mix ure was shaken
gently and let stand 30 minutes prior to reading th: pH

with a glass electrod

 

‘lq{llllil I!

-23-

Organic latter and Total Ash

A 5 gram sample of soil is weighed into a weighed flat
bottomed dish of about 40 cc. capacity (platinum or fused
silica) which has previously been ignited. The dish With
sample is then placed in an electric muffle furnace and
slowly ignited at 500 to 6000 C. over night. Allow to cool
in a desiccator and Weigh. The loss in weight is due to the
loss of volatile constituents, which in peat and muck analysis
is taken as the content of organic matter. Calculate the
percentage of organic matter and total ash in the sample

correcting for moisture content in ese the sample taken

was not water-free.

-24-

EXPERIMEnTAL assJLrs

Table 1. Some chemical characteristics of five acid organic
soils used in the investigation.

 

 

 

 

Lillieguivalents
Aper l00 grams of air dry soil
Total Per cent
Exchangeable exchange Exchangeable base
Soil 4pH hydrogen capacity cations saturatign

 

65.2 81.78 l6.6 20.5

6
2 5.7 62.5 50.4? 17.9 22.5

C)
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0

(0

q n
H

0

01

( J”

0'!

Co

0

«1 03
0')

E C)

O

 

As shown by the data in Table l, the five acid organic
soils differed quite widely in the content of exchangeable
hydrogen.

Each soil was found to possess a high absorptive ca-
pacity for cations and contained a large amount of replace-

able bases.

(D
J
r ‘1
[—1
U)
c1.
(7"
(D
cf
5
(D
:3
L.

A positive relationship was found to
milligramequivalents of bases ar‘ per cent base saturation.
An inverse correlation existed between the pH of the soils
and the milligramequivalents of ex hangeable hydrogen. As
indicated in Tables 1 and 2 percentage base saturation was

found to be closely related to the calcium content of the

soils.

KO relationsnio between on and total exchanne

capacity was noted.

 

 

 

 

Taole 2. '"cha ngeab ble cations and organic matter and ash
contents of five acid organic soils.
Per cent LZilli e uivalents
Organic ner lOO grave of air dry soil
Soil matter Ash ._§a;w Lg K Ea kn Fe

 

 

.015

()1
I.)
O
4:.
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F)
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1 91.0 9.0 15.6

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95.2 6.6 14.5

(‘0

1.2 .804 .010
1

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90.9 9.1 15.4
91.6 8.4 25.9

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C)
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(

F J
FJ

N (O
O O‘- [-4

()1

87.6 12.4 44.9

 

For each of the five soils calcium was found to be
the predominant exchangeable cation. In general, tne cations
appeared in the following order of decreasing magnitude ---
calcium, ma,nesium, sodium, potassium, iron and manganese.

T-e organic matter content varied from 95.2 oer cent
in soil number 2 to 67.6 per cent in soil number 5 and the
ash contents of these two soils were 6.8 per cent and 12.4
per cent restectively.

As shown in Table 2, soil nimber 5 contained the

larzest amount of excnrn eable cations.
t.

I
{0
O)

I

cent total iron, alu::ninun and manganese in
five orjsiiic soils under invest gati on.

 

 

 

1 0.22 0.52 .0056
2 L.16 0.26 .0025
E)

.DO44

L

5
.43 4.70 .0115

UT

 

As indica 'ed in Table 3, the order of magnitude in
which the above three elements occurred in the soils was
aluminum, iron and hen anese. The percentages of the

id not vary to any marked degree between

(L

three ei-ma1ts
so-1s, with the excegtion 0 soil nunber 5 which contained
the largest alcunts of all three of the elements, and was

particularly hi;h in aluminum.

Table 4. Line re dllemlft of th soils as detern ined

by doodrtff's m

 

m . .- , -
101.13 AOL-‘1‘ 2 21C ‘0."

e: il l s 4 5

 

Lime requirement 15.1 15.1 12.5 11.2 7.5

”-0..-

 

 

.VC: 5 run ‘ . - r —’
uoOo,ooC ; M‘UIGS per acre basis.

lime re uiremert is defined as the anount of line
rerqu-a to brira the soil to DB 7.

u L7

in
yfl

e
Dunne"
me

C‘
v

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the
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01
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in
5 Soil

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v.3
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toil num
Soil 1

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etion

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66
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.1-

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d-

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correlat

 

of line TailliTEG to raise tz1e soil ph to 7, es calculated
1y Noodruff's lime requirer 1t nethod, eNd that Obtained
by actual liming. A negative COTTEthiUn ex1sted for

801 s 1 and 5.

Hit} the ex tiC n of coil Limber 1, all the sails
were raised to pi 7 with the edcition of 10 to 1: ans of
lime per cre.

It is evld3nt from data grese1ted in T able 5 that
soil number 1 had a greater buffer capacity than the other
soils. It has l‘een st ated (; 7) that the buffer caeacity
is closely related to soil reeetion are to both ash and
calcium content.

Table 6. The man anese s et‘s of the five organic soils
under in es tigetion.

 

 

 

Perts_per million
Eas ' v Inert
LXCnUn.1able reducible manganese Total
Soil 05 mena: nese r nge1ese oxides ha,;1;ese
l 5.6 25. 13.5 18.7 56.5
E; 3.7 505’ 307 ].'70(-DJ 25.0
5 4.0 5.7 2.5 20.5 26.5
4: 4:05 8‘07 A005 Ji‘.8 44.00
5 5.0 15.0 8.7 85.8 1 2.5

 

Tne manganons—me

soils is shown in the a

11;

b

enic ecuiliorium oi the live or janic

ove table. The exchangeabl

va1ied c01111e~sL1v in the five soils. Tnis was due to
00th the difference in the amounts of total 11n1a 1es e
th¢t each soil 1ossessed and also to t1e difie1e1ce in
soil reactions. 1ne nigh pi values fa ored the oxidation
of the available manganese to the unava'lzole manganic
form.

The amount of ea-i y reducible EC;1CCJCSB for each
of the five 01,1ric soils was relatively small, but was
hi,nes t in soil nur eis 1 and 5 wnicn also contained the
largest anounts of total man; an3se.

There was a 1elative1y small axlount of man

\ganese
fixed as ine't Mnoa in soil number 1 due to its intensely

P.

. - ‘ "va 'V— ‘ TX wr' I;— ~ .. ' - -. ixtrr "n
aCid cna1acter. nonever, tne 1x;n (nese 1 tion has

consicera 13 are; te1 for soil numbers 5, 4 and 5.

 

 

 

 

 

 

 

 

 

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soil QAL the em K>unt oi active 3.0 Qfieie exch sable emf
ea siljr T€d11Cjbl” X102) available for fleet 11: e.

A jositive reletiahshig between the total soil
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men enese iUC“€”S€d with increasinf gercenteges of total

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mesa 1p tn: soil and thc totgl Lam 005$; 11 t10 r000: tLSSJL,
as sn.o,n1:u1'fatles 6 adult: (Fig. 2 .

£8 51000 LA T0010 6, soil number 5 was Aighcst in
t :el.1:un;;;pxa;. lxdug'siy 'the ;:1io;-s'ha1- gstexLLEronlsx Ll

(E:

-. .‘ . 1....-. .' ‘~ ‘. . +- .‘ __- .___1. .9 ;-_.'1 -.‘. _ '..
11‘113001'1, 1". ..LC 1 CL)*L-.)0.L;1€:;-¢ 110.1). Dix: 000011.10 OJ. LCD-00.1“- Lu-.01,_.gl,11.,€

D ‘ ‘. I 2 ‘ r 4 “' “- J I“ In ‘ r ,- 1— .'\ n * a 4' ' \ ‘

1014xi.01 8001 100.c~: -, :00d tuL 10:5.00st 1 KAmeyne oi

no .’ r " F) ." . “ 1- “ .\ r ,’\ ‘~ ‘I l W. - ‘o 1 /‘. 9‘. ‘ ' ‘. “ W n‘ , 4‘ r—j‘ \ .

10000.01m: s 111 (Hat 1 tm1,s. .001 1.11JJS a: t11: LJIKLC; #0000105. .0115
' 40 “‘ -. - A, ' , . L. \ , Tb - 1K, 3 ' {I430 ,. 0.. .. .'- 1.. ' . , ‘ - ‘ .

d1010r0400 1: aCCOdand 103 Ly tae d100000uce lfl {A 01 fine

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-‘lll'l‘

anese in tne plant tissue
from soil nunier 3 whicd contained less total and exchange-
sble monienese than soil number 4, is attributeb-e to a
possible antagonistic effect of calcium since soil number 4
1 '1

r . -' - ‘ r “21, "v: ‘. zw rxmx. 9 ‘ "3 ‘f r” -' \r‘, . " r“! f‘a".‘ "
conteileo neoiiy twi e tne anoint Oi elcnunpceole eloiim.

mL‘lc 0. 'he effect of calcium cerbonete on the content
of total iron, aluminum, and mugsnes in the
elent tissue from soil number 1.

 

 

Grams
Tons of 83003 Per cent Yield of
oei_§cre LA :e Al Mn onion bulbs

“—5

 

 

O 3.6 .17 B.‘ .04 0.33
2 4.1 .03 0.5 .12 l45.“0

 

As shown from the data contained in Table 9, aluminum

C‘
a.)

W

(D

present in the plent tissue in the largest amount both

before eni after the eddition of calcium carbonate. however,

\

the yercentege or aluminum decreased considerably in th—
ent tissue as did the iron, after the calcium carbonate

‘ I- f '4 "‘ 1',“ _ ‘ o r“ "1- \ )\. ‘ - r'r ~. . ‘ .\ - r. \.’-~1‘|— - ,- ‘. y-rx ,' -,
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.1.

-ncreesed in the olsnt tis

m

1";
’ v.

The yield of onion bulbs increased as the gercenteQe

iron sue aluminum cecreesed in the Plant tissue with

)1

increasec cel;ium carboncte an

, r
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m

 

 

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H.nom m.mwun m.®(m o.nmm ©.mpa mmmn ompp orwm mmrm Foam m mogpm

m.moawa mowed armm gamma mammw mmamm nuam. o pzmgpwmua
mzofipwo
m mma mag m -fiammm

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onHmH mdwam moomw mmmom Jomwo ON prOB

 

 

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H

 

 

 

 

m w m m H Hfloa m ¢ m m H Hwom m w m m a Mom mgmw Amp
mmmfimtfiwa mflpfloswmpll mmmgwq1me mapmmwfiHCUKm poa‘qulmemm Koono
ma-mmm .E.m.m .a.m.% udamflk dwmm Mo mace

 

 

.mHHom mgp CH mmewmcmE mapfioscma mafimmm flaw mapw
nwnzwgoxm map :0 Uqw .mpasp doflao we mawflm mgp do mmsondmmmm map :H
. .«30. w ) in- mam undo moo fidao4¢o o s x. .
wagon owd.zao 6H0 q>flw op (QHH m+ Q . r % +omkhm qu .md magma

As shown fro om -ables l0 aid l? a

81 gni1‘i.c alce has tmxnl Obteioed

numbers 1, 2 aAd 5 and significsnce at the

point for soil numbers 4

H

F.)

r-‘J
0

The yield of onio 11

shown in Table 12. The yield of
Innfiber l was
ciam carbonate

the yield of

lie Vield of onion bulbs co 8
Were iHlC eased With calcium carbonate
2 tons respectively. The exchangeable nan

decreased in these soils uit1 increase e6

carbonate.

1
Tne p.p.m.

soils at mciimum Vielos

for soils l, 2, 3, 4 and 5 respectively.

It is shown from these data thst

soil numtexs l, Siznxi.3 were obtsiued

of excnsnje dble msnjcnese was orcsent

U)
L]
(‘3
CM
.3
{a
H
F:
1...

«"1 x C wr'fi’r
VilmLKlnzsl 5:;

.. . 4.x“ . ‘ ..- .. —‘.-
resfiectively. as tut :4 incressed to 4.0

hi;

between trectmei

the onion bulbs
iacxacsed'with the addition of calcium:

treatment.

oil numbers 2,

meximum
when 5.0 to 3.7
in the soil.

nmeels

agu

1

‘ .n"‘ 9

its c: soil

5 per cent

pwlicstion is

On 5011
carbouete

Additional

onion bulbs. The

shown to decrease With

5 end 4

afidd tions 0: :2", 4 and

. "'r‘l " 'r
:,'lt:-.MJS 0A1

9.9.1u

qjllEE $1-1

-40-

numbers 4

CD

" “ :7 2 ,, . . S-s . ‘ . ', “‘ 'I~ .” ‘2 (‘1

J'lu \—' tl’l~:: 1‘). t). 11.1. ‘31 EALCKILLJ-» x: a;ltj 1.1x-«.‘1 90‘461 S 'J C‘s-L S O

I ‘ ~f -. > o a 1‘ . . I“ ‘ ' ... .— '~ 'u I ,-, ’n‘ l ‘ ’7‘ ‘ '.; ,' ~ ‘ '
increased snu nex1mum yielcs Wale olccinec st o.c gnu .c.o
P.y.m. of exc h n13 ole man snese. t is eviuent from tasse

'-I I‘- 7 1' .. J— “ . _ “ " -2 A: ‘h‘ . > J. 1“: ‘ I; 71‘ J .
ngh tdeb an1Lun yielus on 50115 01 an lLbzuSVlJ cc1d

Ht mange-

(in:

ncse than soils "ith 3i values less ficid in reaction.

From these fists 4 to E o.p.m. of e"cn:1. able
H‘l;6;€59 appeared optimum in intensely ecid soils to give
maximum yields; and 6 to ll 3.3.m. o: excnen
Wes Optimum if stron3ly eciu GelditLo (o1 4.6 - 5.1) to
give WWVimum yie lds.

i Oures 4 to 8 show the effect of increLSed calcium
carbonate addition on the onions of the five soils during
their Ferioc of growth. A different growth curve has
obtaine d for cecn soil. Jith the excegticn or soil hunter 5,
all the soils resoundec to tne suciticn of calcium carbonate.
These growth curves are reflected in fig‘re 3 showing the
relation between the yield cf onion bulbs 13d hi.

The bulbs decree 53d in size With increased calcium

carbonste addition after the Optimum smoxnt of calcium had

i)

been reached. As shown in Ii 3u1e b th3 highest fielcs w~'

(...!
'-<
('=
F!

(73

1.x -- ‘ "“ r‘. 3 1-.1|'\J- ~ , A ‘ -'\ ‘r it " r‘ 'q'- " ) ‘ fl .‘ ’-‘ r r . '
obtaincu between tne 9n rcnge of 4.; to 5.3. lion TabJC

-: -' , w .4- 1 -. -, ~ -- 1.. -, -.
it is seen tnet e nclrcc decrease in tic p.y.i. 0: var, ncsc

.../fil—

in the onion LulLS occurred as the soil 9; e,oroocl ed

neutrality and a deiinite manna :zso deficiency re lted.

This was o‘sch:d in th: scrly stsges c IOWth. The

igs c“ ‘hL blents ‘evclcccd s ligd yu‘lon c0101, liter

‘ied anc in sore cases fell off. As snotn in Ts‘le 8

the onion slants tint "cceived the 6, 8, lO and 2 ton

calci- carbonate tVestmen 8 contained verv ttle pg“ .

nes> -11. tl'lcl‘ bulbs. The smell “mounts 01 1:: n, nese in

the cmon bulbs ed the smegtons that occurred dm 1:: thevr
early and late stages of growth indicated tth c deficiency
of vehicles. was a. colxt Lutin- factor towards the low

yields obtain ed from the he evier limed t1 ectrmno. .

Tehle lb. The oftimum pH values 3 ngch the hi3hest
yields wecL obtain 3d fror the 5 cr3Lnic srils
and the .31”... of man: 3a.11-3se contsine" in the

fi .

Tons of
require

CA. .37 , ' ..
oL1l ufl reactio;

of total
ese in

bulbs

p.p.m.

Thy)”: “ v‘ ‘.’1
ilkybApk. .1-

0
01" J (‘11

o-.

 

l 5.0 8 38

2 4.23 8 53

5 5.5 4 25

4 5.0 2 89

5 4.9 0 50
2“There W35 little differe.nce in yield bet esn the 2 ton
and 4 ton calcitm Cerboncte tre stmcnts.

41n-

 

Fig. S-RELATIONSHIP BETWEEN YIELD OF

ONION BULBS AND pH

 

 

 

 

 

 

 

____. 3011 1
_4,¢. Soil 2 ______ _n“
—*—a.— £3011 s * ;;\\.\ f
4“" 58.3% \/ Ni: 4
// ‘1 / .3
/C)/ /’/’Ahfi\\_ f .
\ ”‘x
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f” V j

 

 

 

 

 

 

 

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225

175‘

(71
131.3
:4

U

....a
E?
Bubsin

‘.4‘ ‘~ '
in. (.2113. 03‘.

H
8
1eld

1’ u

{‘0
()1

 

 

 

 

Soil 1.

1 , 2 .
ngi’tg'l".
‘J. \. ’- -‘C;

Fig. 4 - The affect of 11m, OJ tn; -rv.t: of enicns of
soil numler l (pd 3.6). fl - "0 line; 1 - z toys
23- 4 tois;l5-€3tW¢s; 4- tons; 5- (Etonc;
. . c

Soil 2.

Fig.

0"

 

 

‘45

ately 6

01110115 aiipI'Oxlx‘r:
glfifitLug.

mdnths after

0:1 tlh: QLTTVtI; 01
3.7) O - 10 lip:
4 - 8 tu-

fi'h b,_

I419. eff 2:01: 1
SQiJ-1TuILe.r P
- 4 tOnf; d - C tons;

" 1:3 1.30113 0

ii In
(

’
f. C c.
N'1" u

C3 TY)

 

0?

 

 

   

.' “V _' A ' ‘ (‘ ‘ ‘ . J .5. H . . . '._ f v. 47 . ‘ ~ -_ Q ¢.
v'A‘ VU,L.M 1 .L 4‘-.. J.,_.- k: ~2..I.J. - ..L .I--.. [LIL/e V’J.
J- J.

. .I —. 3.. ..

illCLJL-t l1“.-.
\—
ms 11) _ +1
,\ Ir\ fx‘

- IIe e: :01". 1-4.
G
g!

" “ n I q. I ‘ \ ‘
:J )(,).~t.l OJ. J11~L3AJS CI
.: .. ”1,-— , ‘ A
G-L - 117.13.436.13 v (:3'.‘ LEGO).

C‘» - no liI,'_s.-;; -
tone; “.5 — 6 tons; 4 - 3 tons; LI - 10 t
tons.

‘7‘
0‘}
6 -

H J3

(T

 

 

Cl t‘sI-z': -_‘I'O‘..'t':1 of on'ons

R C; ,» ’ ° \
4w). 0 - I10 1.11%; l -
tons; 4- - ‘c'. tons; £3 - lO

 

«b

CO

(I)

 

 

I

Grcmth of onions l4 weeks after 6

ate 0: glanting.

 

 

 

 

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. ' - “-3 ".‘rvn ‘ "17 ‘s ‘A'\ - "- ‘ N- ‘VI *— f .
011:.01'15 'cxr‘yi'OJ-J.I2L,LD_LJ? L III\)JIt..lS (LIT/€51. Lube Of

planting.

The effect of lime on the growth of o _

soil Dumbe“ E (93 5.0). O - no lime; l - 2 tan
2 - 4 tone; .5) - 6- 1301-5; 4- - 8 13015 5 ’
6 - 1; 130115.

~466-

 

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-47-

DIS CUL IL'C‘I!

The exieri.cntal results I:Ies ented have shown that

y

the go cle factors affecting the resgcnse of different
acid 01 chic soils to life agglication are numerous.
Tlie lime re lilcmcyt as detecrine d bv noodru f's

method (il) agreed closely with the actual an; unt of

(7‘
L .1
.J
T
C;
f
H

calcium carbonate reguired to raisw V of soils 2, 5
and 4 to 7.0, but failed to correlate with soils 1 and 5.
This lack oi rel; tich.ii was possih v due to the greater
buffer cagacities of these tw soils if the amount of
calcium carbonate that is required to bring the soils to
any hiuher pH value may be used as a measure of buffer
caiacity. High acidity and a low content of bases are

associated with high buffer capacities as measured with

The per cent base satu'ation and total exchange

capacity are ye PhEvS better criteria tIan pH for estimating

.Cl

leS

d.

lime needs on organic soils. The base exchan-e c;o

-.
I
C} .L

m
m

of the five organic soils used in this study did not vary

1

to any nthto de .gree and thus it Ias possible to make

m

good com;arison in their lime requirements.
The importance of Optimum base saturation was shown
by the yields obtained on the unlimed treatments of the

five organic soils.

-45-

Percentage base satu r~tiozI v.35 found to be closely

related to the calcium ccnte nt of the soils and it has
found (Ii5. 9) that tl'Ie yield obtained on the unlined
treatments were a function of th— millia1uivalents of

e“ hangeatle calcium present. The yields inCIea sed with

iIcreas ed amounts of L"c1 n‘eaole calcium up to the point

yields. It

where additional calcium inhibited increased

.e 1usnt:3ties

t
's—I

has been pointed out (E) that cougaratively la r
of calcium are essential to glant 5rowths IId hat normal
absorption of other ions degended on a certain minimal
quantity of calcium ions. However, from the results ob-
tained in this study and from the work of others (9, ll,
17,18, 50) the addition of excessive amounts of calcium
to the soil have r.s ulted in decreased availabilities of
many micro-nutrient eleme rts esgecial y manganese and iron.
The man aIIese status of the five organic soils was
found to vary considerably as show by t'le data Presented
in Table 6. There was relatively small amounts of man5anese
fixed as inert oxides in soil l, due to its intensely acid
character. However, the fi} z:tion of manhaIese :as consider-
ably hi5her for soils 4 and E. Inis resulted from a decrease
in acidity which favored the oxidation to the manganic form.
The amount of easily Ieduciole mazganese was relativelv
small in all soils but was hi5hest in soils l and 5 which

also contained the lar5est amounts of total manganese.

9-

L5!)

The large” ¢:1oum1t of exchangeable and easilv
reducible m;njanese in soils 1 and S accounted for the
greater gusntities of total manganese contained in the

onion tissue herv sted from these so: Lls.

(D

Sherwen (14) has stated that in any alkaline soil
at least 5 p.p.m. of exchen3eeble Tdn11ncse 1n1st be gresent
for satisfactory crop prod ducticn and in order to maintain

edemiu te level of the exchangeable fraction this mus t

7
‘1
....-

O”
(D

supglemented by et lee st 100 p.p.m. of e esily reducible
‘snese. In acid soils, however, the Optimum level of
eXCQofl”UCLlG me_n; enese can be much lower, with the amount
degending on the egree of acidity.

From the data presented in Table 6 it was shown
that the total n n33. 1es e for ev;rv soil with the exception

of soil 5 to be les

(0

then 100 p.p.m. and much of this was
In res u1t in the inert form.
No manganese def cfi.er1cy existed in the olent tissue,
however, Where no calcium carbonste was egpliel. It agpeers,
therefore, that suiii cient meng3 enes e was available to the
plant clthl’l t1ere mes a small amount of ees ilv leducible
menlu1cse in the soil. nith centinued croggiug, however,

[I

‘1 I r .1. "0 ~ ‘. -"_‘ \ ‘1' ’~‘ ‘ ‘, ‘ fl ,‘1' “1‘. a“ j 'K " " 9"".
this smull 1es ive CL Leh3snese wodlu GVbAtUQlly LCCUmb

(I)

depleted and additional nsn3enese w uld be required, usually

epglied to the soil as manganese sulfate.

-50-
The exc1unueeole m n Cncse decree ed in tie five
organic soils with increCsed calcium carbonate a3.1pli CCt ions
and pH. In cert, the excheniesble nCnfiCnese was depe1de nt
upon the tonal manganese in the soil, as showu in Ei3. 1.
This Iel ti311° hip, however, was associated wjth the pH of

geuble

the soil. At low pd values the quantity of exchen
men3Cnese was a function f he totCl soil mengenese and
increased “'o1ort10uCt lv with tl1e increz se in total 8 il

manganese. at higher pd values, however, th:r was less

exchsn3eeble an3Cngse gresent in soil number t even though
it cortsined the lCrgest pe“centC3e of total nun3u1ese.
High pd values favor the formation of the unavailable

0" r-r~ . (t-“V-r"fl "= y‘ .. P~ r- 4” .fl‘rq'; J "r f‘\ 1: o,'l',“".,
men onic Muhrafluub Wdllc Cold ConditiOHs ever the f01nution

In

of the availele monfenous form. It has been stated (to)

I.

that the differe 1ce in ("cvwgeeble 111C1113Cu1esle - s due to the

r.

V —~ ‘.- A w r ‘ I‘ I 11 -' a g - , -_—~ , 1' 1 ~.' . ' -\ . \
e£C1Cn e be u—en toe stsorbed LCnCCnese one celc1un thS
o . ~ ~ + o ." f‘fi- A ‘ c ‘ o ‘ -f _: I x" P. 1 ...‘
in too soliCion. 11C result is C gTQCIPAtEtLDJ o: tns

"1 .,,1- .~ If...» 1.." .n -. .1— -m- ~11
IOIner cCtion Cs insoluble an3Cncss nfuroxi e anCd mzv

‘

0
ti
t"
H
C)

be oxio ized t
A relC— ti onsl1io ties eviient between total m'C‘1113C.1ese
in the plent tissue and total soil 113enese. Soil nimbel s
l and 5 contained the highest percente3es of totCl soil
1enanese and the ; Cnt tissue hervested from these two

soils was also the higuest in totCl men Cnese. This

-51-

relCtionshig, however, is i1flluenced pi, Circe the

~r1 ma ‘
elchn13eC13-e an Ch

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fl . t: ’1 3 _ C r- 1‘ . I_1 1 ‘ ‘ C . Vl' r‘
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pracomin1Cntl" governed by the pH of the soil.

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In a gene1C wev tdd dCCC uLVb sho n tuCt the eCsily

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PSdUClLit m AMLHQS: n ICCSed cs t3: '“CALE Cble :Cn1Cnese

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at stron3ly acid CON(lt"OuS, however, such a soil reaction
WOle nzt be inducive to good lent growth. Additions of
S"lfur to ClkCline mucks nCve uermunently lowered t11e 03

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the 1111:. 'CilC-ble conditf o 1, 1118'1”€1111C mangCnes-e.

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It has teCn shown (14) that 'n alkaline soil at

5:. I 7‘ , "' vr r r-r‘r‘“ "\ 1‘ :- fl 1 14f“-
CCs o .1.m. o1 e-chn3eetl, rCng-nsse mu t be 31es-nt
for SCtisiCctcry cro; broiuctlcn. liror t11esC d3 ta it 18

observed t the exchnserle or nCnrsn013 zen Cnese

.- p‘r‘J A n f“ r ... . o \‘ _. C r-
becon1 ‘cllClEnt (less u 3.3.x.) Ct C331OXiLC-ely 11 u.C.
\ ”"r . " .Ar r" ~“I "’\r . -* —‘: x - J“ «1 A
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tchC1CeC;le an3Cnese :ell off rC3idl
to tel. 3C13C' 11es WCs founu to be
CreCtest in the leres of the 3lCnts. The ratio of men3C—

‘ . ' ‘ 1 ' “ 4" I. (4 ' "‘ ~\ -" ‘ 1’ F ' " "o ""' “‘~”"‘ ‘1
nese in tie 1CCVes b0 tnCt Oi tdz oilts mes C.110111C eCy

'w '1 ‘4. w . . A- . 'T ,- -. .ol -., 4 n ‘ ,r v.3

lozl at t;e lower p4 values ior sol s l, s and 4 as cengaied
(- v A - .- A «y; - . i -,N- “I x1 a:

to 3:1 at ta: niLner 34 values ior SQllS l, u, 4 and c.

' ‘ '.~ V. ' -‘ "' ‘ ‘ ’w -';.,‘~.",‘ 1"‘.' « '
inis snois tnat LUST, of tne .1852: is

prom the analytical data of the onion tissue harvested
from the non~limed treatment of soil number 1, p? 5.6, it

has been shown that iron aid aluminum were yresent in such
quantities as to be toxic to the plant. The addition of

two tons of calcium carbonate to soil number 1 decreased

the amounts of iron and aluminum in the glant tissue, as
shown in Tatl1 9, and the subseguent onion yields were
increased fnom .oé grrns to 15 grams resoectively. Crist (3)
and Hardenburg (lb) found that applicatio s of lime greatly
reduced the intake of iron and aluminum by the tlant. From
the results obtained, manganese does not appear to be the
toxic micro-nutrient element since it gas actually present

in smaller quantities in the plant before tne addition of
calcium carbonate than afterwards. Tne increased manganese
content subsequent to calcium carbonate addition is converse
to the other results obtained with manganese availability.

It is Lnomn, nowever, that an encess amount of aluminum

has caused a renuction in the absorption of all materials (33 .

-50-

The reduced quantities of soluble aluminum in the soil after
the additiOn of calcium carbonate offers a gossible exolana-
tion for the difference in manganese content of the ,lant
tissue before and after calcium carbonate additiOn.

Aluminum toxicity or a combined toxicity of aluminum,
iron and possibly manganese appears to account for the low
yields obtained from the unlined treatments of soil numbers
1 and 2 which had pH values of 5.6 and 5.7 resgectively.

As shown in Figures 4 and 5 the onion plants were dwarfed
and the roots produced few branches.

As shown from the data in Table 1% calcium carbonate
significantly increased the yields of onions on soils 1, 2
and 5 (1% level) and at the 5 per cent level between calcium
carbonate treatments on soils 4 and 5. The unlined treat-
ment on soil number 5 gave significantly higher yields
over the limed treatments and this was the only soil that
did not resgond to calcium carbonate addition. Soil number 5
was 85 per cent base saturated before liming, aboarently
increased additions of calcium carbonate decreased the
absorption of the micro-nutrient elements and esoecially
manganese as shown in Table 8.

Although there was no direct correlation between
the yield of onion bulbs and manganese content there

apneared to be a definite trend in this direction.

-54-

With the exception of the unlimed treatments (check
treatments) of soils 1 aid 2 the heavily limed treatments
gave the lowest yields and they also contained the lowest
amounts oi man ahese; however, some of the treatments that
also gave high yields contained low amounts of manganese.

Results have shown, Table 25, that the highest

" ' '1 in ’L' "o "‘1“ ‘:‘ ‘1. V A A . :r 1" f" ' r x ‘ A V 'r .7»:
chlu lOl the live soils tere Obtained betaeen pn 4.20

U)

and 5.5 and the Optimum pH approximated 5.0. The manganese
content in the onion bulbs obtained from the soils uith the
highest yields ranged between 22 and 50 p.p.m.

The data hsve shown that it is important to recognize
not only the beneficial effects of calcium, applied in.the
form of lime (calcium carbonate) in optimum amounts but
also possible detrimental effects associated with overliming.
While the need for lime is recognized as a recommended soil
management piactice, the addition of excessive amounts of
lime to a soil should be avoided in order to prevent the
inducing of certain micro-nutrient element deficiencies,

notably manganese.

SUHQAHY

This study was instituted to determine the effects
of calcium carbonate addition on the manganese status of
five acid organic soils and to investigate a number of
factors that might be associated with the causes of
variation on the reaponse of different acid organic
soils to lime applications.

Five organic soils of varying acidity were obtained
from different locations in hichigan. The soils were dried
to an apparent Optimum moisture content and each soil was
sieved through a 1/4 inch screen. Determinations of pd
were made on duplicate samples at a previously determined
moisture content by the glass electrode method. Lime was
added to the soil in 2 ton increments resulting in soil
treatments varying from 2 to l2 tons per acre. Each treat-
ment was replicated three times. An unlimed treatment was
included in each case.

A basic treatment of 2,000 pounds of 3-9-18 fertilizer
and 100 pounds of copper sulfate per acre was added to all
the treatments of the five soils.

On January 19, 195l, the jars were seeded 5/4 to

1 inch deep with Brigham's Yellow Globe, a medium maturing

-56-
variety of onions. The onions were harvested on June 21,
1951. Air dry weights of the tops and bulbs were recorded.

The untreated soils were chemically analyzed for
the following constituents: Exchangeable calcium, magnesium,
potassium, sodium, manganese and iron, and total iron,
aluminum and marganese. In addition the following properties
were determined: pn, exchangeable hydrogen, total exchange
capacity, exchangeable cations and per cent base saturation.
The lime requirement for each soil was determined. Exchange-
able and easily reducible manganese and pH were determined
on the soils after treatment with calcium carbonate and
following the harvesting of the onions.

‘ Total manganese determinations were made on oven-
dried tissue from the tOps and the bulbs of the onions.

The following observations were made from the
investigation;

1. The per cent base saturation and total exchan
capacity are perhaps better criteria than the pH value for
estimating lime needs on the organic soils investigated.

2. Percentage base saturation was found to be
closely related to the exchangeable calcium content of
the soils.

5. The yields of the unlimed treatments increased
with incr ased exchangeable calcium up to the point where

additional calcium inhibited increased yields.

4. The exchangeable manganese decreased in the five

organic soils with increased calcium carbonate applications

5. There was a positive relationship between exchange-
able manganese and total manganese in the soil in strongly
acid conditions, however, this relationship did not nold
at higher pH values.

6. There was some indication of relationship between
total manganese in the plant tissue and total manganese in
the soil, however, this relationship was id part dependent
on the amount of exchangeable manganese present in the soil
which varied with pH.

7. In a general way the easily reducible manganese
increased as the exchangeable manganese decreased with
increased calcium carbonate applications.

8. All five soils had sufficient total manganese
to supply adequate amounts for good plant growth, but
under a continuous crOpping system additional manganese
would be required.

9. In every case the total manganese was found to
be greatest in the leaves of the plants.

10. at intensely acid pd values (5.0-3.9), the iron
and aluminum were present in the plant tissue in sufficient

amounts to be toxic to the plants.

-53-

ll. The addition of cal ium carbonate decreased
the amounts of iron and aluminum in the plant tissue.

12. A high significance between treatments was
obtained with addition of calcium carbonate on soils 1,
2 and a with pH values of 5.6, 5.7 and 4.0 reSyectively.
It was not advantageous to lime soils 4 and 5 which had
pi values of 4.5 and 5.0 resgectively.

15. Although there w s no direct correlation
between the yield of onion bulbs and manganese content
there appeared to be a definite trend in this direction.

14. The highest yields for the five soils were
obtained between 9H 4.2 and 5.5 and the Optimum pH
ayproximates 5.0. The manganese content of the onion

bulbs which gave the highest yields ranged between 22 and

10.

-59..

EIELIOGRAPJY

Blair, A.W. and A. L. Prince, 1956. Manganese in New
Jeis ey soils. Soil Sci. 2(5): 527-555.

Bray, 3.3. and F.x. Uillhite, 1929. The determination
of total refilaceable bases in soils. Ind. Eng. Chem.
Annal. Ed. 1: 144.

Crist, J.W., 1925. Growth of lettuce as influenced by
reaction of culture medium. hich. Agr. Expt. Sta.
Tecn. Dul. 71.

Davis, J.F., 1950. Much soils when bronerly fertilized
oroduce high yields. Amer. Plant Food Jour. 4: 5-11.

Davis, F. L. and C. Brewer, 1940. The effect of liming
on the absorption of uhOSJhorus and nitrogen by
winter legumes. Jour. Amer. Soc. Agron. 55: 4 4-462.

Drosdoff, M. and D. C. Nearpass, 1945. Quantitative
micro-deterrination of magneSium in ,lant tissue
and soil extracts. Ind. Eng. Chem. Anal. Ed. 20:
675-674.

Dunn, L.E., 1944. The effect of lime on the availa-
bility of nutrients in certain western aashington
soils. Soil Sci. 56: 287-516.

Emmert, E.L., 1951. The effect of soil reaction on
the growth of tomatoes a' ulettuce and on the
nitrogen, phosphorus and manganese content of the
soil and plant. Ky. Agr. EXpt. Sta. Res. Bul.
514: 85.

Funcness, E.J., 1915. The develonment of soluble
manganese in acid soils as influenced by certain
nitrogenous substances. Ala. Agr. Exgt. Sta.
Bul. 201.

Ge droiz, K.K., 1926. The investigations of K.K. Gedroiz
on base exchange and absorption. A resume. Internatl.
Soc. Soil Sci. Trans. Second Comm. A: 195.

ll.

(A
ltd O

14.

16.

17.

}...J
1.)

19.

-60- ‘
Gilbert, B.E., F. T. TcLean and L.J. Hardin, 1926.
The 1e1atioi oi marganese and iron to a lime
induced chloros' 3. Soil Sci. 22: 457.

ii Lssinn, D.J., 1926. Uhat nagzehs to the lime when

soil is limed? Internatl. Soc. Soil Sci. Trans.
Second Comm. A: 174.

, 19 6. The relation between the
values pd, V and (humus) 01' some humic soils.
Internatl. Soc. Soil. Sci. Trans. Lecond Comm.
A: 195.

TU) DD

harmer, P.m., 1941. The mucl: soils of nichigan,
their management and uses. Mich. Agr. Empt.
Sta., Snec. nul. 514

hardenbu‘g, E.V., 1925. Luck soil reaction as
related to the gro.;th 01 certain leaf Vegetables.
Plant Physiol. 5: 199-219.

Jacobson, H.G. and T.R. 5W? “aback, 192s. Kanganese
toxicity in tobacco. Science 72: 255-224.

Lynd, J.Q. and L.H. Turk, 1945. Overliming injury
on an acid sandy soil. Jour. Amer. Soc. Agron.
4:0: SOL-4: E.

Iann, h.B., 1950. Availability of manganese and
iron as affected bf afglications of calcium and
magnesium carbonates to the soil. Soil Sci. 50:
117-151.

McGeorge, ‘.-L’.T., 1950. The base ex'hange nroyerty
of organic matter in soils. Ariz. Agr. EXEC.
Sta. Tech. nul. 50: 151-215.

Lcflargue, J. 8., 1922. The role of manganese in
91.8.1113?) 0 J01}; o ." m‘n‘ELl‘. 8.1».1110 SOC o 44:11,.125.

, 1925. Effect of different
concentrations of manganese sulghate on the
growth of plants in acid and neutral soils and
the necessity of manganese as a plant nutrient.
Jour. Agr. Res. 2 : 751-794.

m
01
O

27.

’3’)
O)
o

(1”

29.

‘1

5}}

-51-

McLean, F.T. and B.E. Gilbert, 192 . The relative
aluminum tolerance of crop plants. Soil Sci.
24: 165-174.

Moser, F., 1942. Calcium nutrition at reapective
pH levels. Soil Sci. Soc. Amer. Proc. 7: 559—544.
huller, J.F., 1955. Some observations on oa. exchange
in organic materials. Soil Sci. 55: 2*” ‘

Naftel, J.A., 1957. Soil liming investigations:
The influence of lime on yields and on the chemical
composition of slants. Jour. Amer. Soc. Agron.
29: 557-547.

Official and tentative methods of analysis. 1945
Ed. 6, Assoc. Official Agr. Chem., Jashington, D.C.

Pioer, 0.8., 1951. The availability of manganese in
the soil. Jour. Agr. Sci. 21: 762-779.

Pierre, W.H. and u.n. Allaway, 1941. Calcium in the
soil: biological relations. Soil Sci. Soc. Amer.

Pierre, N.h. and A.D. Stewart, 1955. Soluble aluminum
studies: IV. The effects of phosohorus in reducing
the detrimental effects of soil acidity on plant
growth. Soil Sci. 56: 211-225.

Prince, A.L. and S.J. Toth, 19 . Studies on behavior
of manganese in the soil. S111 Sci. 46: S5.

Remington, R.E. and 3.3. Shiver, 1950. Iron, cougar,
and manganese content of some common vegetable foods.
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Russell, Sir E.J., 1955. Minor elements in slant
nutrition - hanganese. The Jour. of the Royal
Agric. Soc. of England 99: 555. From minor
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Schollenberger, C.J. and 3.5. Simon, 1945. Determination
of exchange capacity and exchangeable bases in soil -
ammonium acetate method. Soil Sci. 59: 15-24.

41.

_ C)
-' A)

Sherman, D.C. and P.H. Harmer, 1942.
manganic equilibrium of soils. Soil
Amer. Proc. 7: 598-455.

Toth, S.J., A.L. Prince, A. Wallace and D.S. Hikhelsen,
1946. Rapid quantitative determination of eiéht
mineral elements in slant tissue by a systematic
procedure involving use of a flame bhotometer.

Soil Sci. 66: 459-466.

Triog, E., 19 8. Soil acidity. 1. Its relation to

the growth of olants. Soil Sci. 5: 169-195.

Wilson, B.D. and E.V. Staker, 1955. Ionic exchaxce
of pea soils. Cornell Univ. Agr. EXpt. Sta.
Memoir 172: 1-15.

combosition of the muck soils of New York. Cornell
Univ. Agr. Expt. Sta. Bul. 557: 1-26.

Willis, L.G. and J.O. Carrero, 1924. Influence of
some nitrogenous fertilizers on the develooment
of chlorosis in rice. Jour. Agr. Res. 24: 621-640.

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Hoodruff, C.H., 1947. Determination of the exchangeable
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Soil Sci. Soc. Amer. Proc. 12: 141-142.

{.11
1111 ( fl‘l‘l‘. '