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All Graduate Theses and Dissertations
Graduate Studies
Winter 1-1-1956
The Effect of Bicarbonate on the Uptake of Zinc by
Plants
Lawrence G. Morrill
Utah State University
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2702.
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THE EFFECT OF BICAROONATE ON THE UPTAKE
OF ZI ~ BY PLANTS
Lawrence
o.
Morrill
A thesis submitted in partial fulfillment
ot the requirements !or the degree
ot
KASTER OF SCIENCE
in
Soil Physics
UTAH STATE AGRICULTURAL COLI.Em
Logan, Utah
1956
31f~
1 f!5e.
e. ~
ACKNOWLEOOMENT
1 wish to express ra:r sincere appreciation to Dr. Sterling A.
Taylor for his advice and assistance.
1 also wish to express my
thanks to the Atomic Energy Commission
~hose
funds have made this
study possibleo
Lawrence G. Morrill
TABLE OF CONTENTS
Page
Acknowledgment
Introduction
•
•
Review of literature
•
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Zinc deficiency disease
Zinc vs. the soil
• •
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11
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21
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22
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Soil reaction
• • • • • • • • •
Soil type
•
• •
Soil ~ospbates, calcium, and carbonates
Formulation or the problem
Experimental methods
Results
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Preliminary experiments
•
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Bicarbonate-zinc-plant relationship
Corn
•
• • •
Tomatoes • • • G
Statistical analysis
Discussion
. Summary
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Literature cited
Appendix
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5
25
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26
•
29
Data and statistical analysis tor uptake of zinc by corn
in a six-hour uptake period
• • • •
• • •
Data and statistical analysis tor uptake of zinc by
tomatoes in a 12-hour uptake period • • • • • •
29
31
LIST OF TABLES
Table
1.
Page
Approximate amounts of H2co 3, HCO), and ooj present under
different conditions of pH and nominal bicarbonate levels
10
UST OF FIGURES
Figure
1.
2.
).
4.
5.
Cutaway diagram of experimental apparat\13 for the study
of zinc availability vs. bicarbonate • •
•
•
12
Regression lines representing the data plotted of zinc
uptake by corn in 24 hours as a function of pH with
the pH being controlled by two systems; KH2P04-NaOH
and barbital-HCl buffers
•
•
•
•
16
Zinc uptake by tomatoes in 12 hours as a function of
pH at a constant nominal bicarbonate level
•
•
•
18
Uptake of zinc by corn in six hours as a function of
nominal bicarbonate concentration at a given pH
• •
•
19
Uptake o! zinc by tomatoes in 12 hours aa a function
of nominal bicarbonate concentration at a given pH
•
20
INTRODUCTION
Zinc deficiencies occur in many fruit orchards in Utah even
though the soil contains amounts of zinc that would normally be
sufficient for good plant growth.
The existing zinc problem in Utah
is 1 therefore, one of availability.
Problems of zinc availability generally occur in the pH range of
6-8. Zinc deficiencies occurring within this pH range are 100re
frequently found on well-aerated soils than on poorly aerated ones
with other conditions being the same.
It has been shown that carbon
dioxide will convert both zinc hydroxide and zinc carbonate into more
soluble bicarbonates with the concentration of zn++ that is converted
being a function of the carbon dioxide concentration (28).
It is also
known that if carbon dioxide is dissolved in solutions with pH values
of 6-8 the predominate ion resulting will be bicarbonate.
These facts
suggest that one of the chemical species present resulting from dissolved carbon dioxide might be closely related to the problem of zinc
availability.
Other studies have attempted to relate zinc availability to such
factors as alkalinity, soil colloidal content, organic matter 1 and
simple precipitation and have been successful in explaining the
situation in some areas but do not seem to elucidate fully the conditions in Utah.
This study represents the first attempt, as far as
can be ascertained, to correlate zinc availability with bicarbonate
ion concentration.
2
REVIEW OF UTERATURE
Zinc deficiency disease
The indispensable nature of zinc to the growth of higher green
plants was suggested by
Maz~
(27) in 1914 from his work with corn.
Sommer and Lipman (38) and Sommer (37) proved that zinc was essential
for several field crops.
At the completion of his work , Sommer
hypothesized that zinc was necessary for normal growth of all higher
green plants .
Most of the work establishing the essential nature of zinc to
plants was done in a ten-year period, starting in 1926, in the South
and southeastern portion of the United States .
Not only was the
essential nature established but quality and yield were improved by
addition of zinc salts to crops.
In addition, the diseases commonly
called trenching, mottle lear, little leaf, rosetting, bronzing of
tung oil trees , and white bud of corn were all found to result from
zinc deficiencies (1, 2, 9, 11, 22, 29, JO).
Zinc deficiencies have
since been reported throughout the fruit growing regions of the West
(44) .
Zinc vs . the soil
Zinc deficiencies can be separated into two general categories
according to the type of soil on which it occurs.
One category
appears to be an actual deficiency of zinc in the soil as a result of
crop removal and leaching.
The other type occurs mostly on neutral or
alkaline soils where the supply of zinc seems adequate but is unavailable to plants in sufficient quantities for normal growth .
It is the
3
latter problem that prevails in Utah.
Therefore, this study has been
largely confined to material related to unavailability.
Soil reaction
In generalizing concerning zinc
deficiencie~
and soil pH, several
workers have noted that deficiencies occur on neutral or basic soils
even though the zinc content
u
higher than would be necessary for
normal plant nutrition under acidic soil conditiorus (1, 8, 9, 10, 15,
25, 31, 35).
Brown (7} suggests that these deficiencies may result from the
adsorption of zinc as (znlR) .. on soU colloids or precipitation u
Zn(OH)2•
Precipitation as Zn(OH) 2 is inferred also by Camp and
Reuther (9}.
They noted special trouble with deficiencies on calcar-
eous soils at pH values from 6.5 to 7.5.
'Ibis suggests precipitation
in insoluble forms 1 according to El.gabaly (14) 1 although he feels there
are other possibilities for explaining the results.
Peech (31) found that as the pH decreased in the soil, more zinc
could be extractable with normal NaCl.
Epstein and Stout
(15)
analyzed supernatant liquids from a series of bentonitic cultures.
They found an increasing amount of soluble zinc with increasing
hydrogen ion concentration, which is in agreement w1 th the findings
of Peech.
Camp ( 8) concluded that the availability ot zinc decreases with
increasing pH up to a critical range from
range zinc again became more available.
5.5
to
6.5. Beyond thi~
In his study of zinc release
!rom clay, Jurinakl induced al.kalini ty1 using potassium hydroxide and
r.
Jurln&k, J. J. 1954. The available forms of zinc in alkaline
soils. (Jl. S. Thesis. Dept. of Agronomy} Utah State Agricultural
College.
4
found a minimum i n the release curve from pH 5 . 5 to 1. 0 .
Lott (25)
showed that only at pH values below 6 do toxic amounts of zinc
a ppear in s ol utiono
He aLso states that the amount of zinc in solu -
tion does not r each a mi.nitrum u ntil a pH of s omewhat higher than 6
is reached.
Some non-calcareous soils of utah show deficiency signs
at pH values of
6.5
to
7.5 (41, 44) .
Chandler (10 ) stated that deficienci es rarely occur in soils with
a reaction between pH 8 and 9 except on old corral spots .
b,y Camp
The mention
(8) of possi ble zincate formation at a pH above 7. 85 lends
support to Chandler ' s statement; however, increased u ptake of zinc in
this pH range finds opposition in Truog ' s
of
6.5
Soil
(43) assertion t hat the pH
is optimum for the uptake of all plant nutrients .
~
Zinc i s fixed in unavailabl e forms in some soil s more readily
than in others.
This fact is commonly correlated with the col l oidal
content of the soil.
Clay and organic matter were found to be
important factors in zinc fixation by Chandler, Hoagland and Hibbard
( 20 ), J ones, Gall and Barnette (22) , Camp (8), and Baumann(4).
Baumann f ound tha t organic soil had the greatest power for fixation,
with clay and calcareous s oils c oming second.
He concluded that
humic acids , zeol i tes , aluminum hydroxide, and carbona tes of calcium
and magnesium were very effective in removing zinc from solution.
El.gabaly (14) f ound that zinc c ould be adsorbed as a monovalent
cation and become part of the elec trical double layer.
dition it could not be exchanged with neutral salts .
In this conAfter replacing
magnesium in the crystal structure by zinc , Elgabaly found that the
process was not reversible and that part of the zinc was fixed in the
s
clay lattice.
Hibbard (17) postulated that zinc could be substituted
for magnesium in the tetrahedral or octrahedral position of the
alumino silicates and that the replacement of zinc in this structure
t
I
I
would only be possible by the small hydrogen ion.
The idea that zinc
may replace magnesium in the clay lattice is not supported by Kruyt
(23).
He states that exchange of lattice ions is highly improbable
except in newly formed precipitates.
The replacement of zinc by
hydrogen ions indicates that zinc has added on to the lattice or has
taken position in holes in the lattice and not exchanged from the
tetrahedral or octr ahedral positions; however, both possibilities
would entail a strongly adsorbed potentially dete:rm:i.ning ion mechanism.
This mechanism would also expl ain why Brown ( 7) 1 Epstein and Stout
(15) , and Peech (31) found hydrogen ion more effective in replacing
zinc than neutral normal solutions.
Soil phOsphates , calcium,
~
carbonates
The occurence of high soluble phosphates in areas of zinc
deficiencies suggests that zinc may be tied up in some fonn of insoluble
zinc phosphate .
This idea is supported by the research and observa-
tions of several workers
(4 ,
11, 22, 30,
44).
The prevention of zinc deficiency symptoms in fruit trees by
intercropping with alfalfa was interpreted by Chandler (10 ) to result
from the high phosphate feeding capacity of alfalfa.
Chapmann,
Vanslow, and Liebig (12) noted a high phosphate zinc deficiency relation
in growing citrus plants in nutrient culture.
In some soils the zinc
level is high enough to be toxic to plants, and in many cases this
toxicity has been aleviated by applications of lime and t*tosphate (3,
16, 25, 39, 4o).
6
Peech (31) has shown that phosphates are not responsible for zinc
and copper fixation in Norfolk fine sand.
Jamison ( 21) states that
this conclusion is true in general for the citrus growing areas of
Florida, unless excessive amounts of phosphates are applied.
The data
presented in a paper by Boawn, Viets and Crawford (5) do not support
the idea that phosphates have an adverse effect on zinc adsorption or
utilization.
They state that phosphates had no effect on applied zinc
or native soil zinc.
A study of the effect of phosphates on uptake of zinc by excised
barley roots by f earson2 indicates that phosfhates reduce the uptake
of zinc only at fll values above 9.0.
He also studied the effect of
calcium and found that the presence of small amounts of soluble calcium
appreciably reduced zinc uptake.
He then postulated that the adverse
effect noted upon applying superphosphates to the soil is traceable to
the calcium associated with such an addition, and the effect resulted
from competition between ca++ and zn.l.+.
The presence of carbonates and lime minerals in the soil has been
cited as the cause of high zinc fixation
(h,
33, 34, 37), and calcium
hydroxide was noted to have a greater effect than calcium carbonate ( 39) .
Powers and Pang (32) performed an experiment to determine the form
in which zinc should be applied to the soil.
ZnC03 .
They used ZnS04 and
Zinc chloride was used as a check for the addition of sulfate.
Zinc carbonate was just as effective in supplying zinc for plant growth
as was Zn004.
Shaw, Menzel and Dean (35) performed a similar experi-
u.3nt with the same results and they stated, "If fixation of zinc does
2.
Pearson, G. A. 1951. Some factors influencing absorption of zinc
by roots from single salt solutions. (Ph. D. dissertation.)
University of California. Berkeley.
1
occur in the soils the high solubility of zinc sulfate makes it
especially subject to such a fixation reaction."
Strong adsorption of zinc from solution on the surface of lime
minerals (calcite, magnesite and dolomite) was demonstrated by J\.o.rinak3.
He expressed the opinion that zinc could extend the
fit into empty sites in the lattice.
c~stal
lattice or
This would be possible because
the unit lattice of zinc carbonate is very simihr to that of magne sium
carbonate.
3.
Jurinak, J. J. (195~) The effect of temperature on the adsorption
of zinc by calcite, magnesite and dolomite. t'aper to be presented
at American Society of Agronomy meetings. 1955.
8
FOIDtULATION OF THE PROBLEM
If zinc availability is increased in the presence of bicarbonate,
it would be difficult to determine i f bicarbonate itself was the cause
for this increased availability or one of the two chemical species
(H2CQ 3 or COj) in equilibrium wi til it in solution.
Even though the
amoUftts of H2003 or COj present might be quite small, their presence
and the possibility that they may react with zn++ and increase its
availability should not be overlooked.
It is difficult to determine, chemically, the amounts of one of
the species resulting from dissolved carbon dioxide independently of
the other two, and it is also difficult to maintain their concentrations
constant over a period of time.
Because of these facts, the experi-
ments run using bicarbonate were evaluated on the basis of the amount
of bicarbonate added to the experimental solutions.
The term "nominal
bicarbonate" is used to denote this added amount of bicarbonate, even
though it is present as three different cher:dcal species (H 2co 3 , HCOj 1
and COj) •
Despite the fact t..l-}at the ammmts of these species present
varies under different conditions, the "nominal bicarbonate 11 level
affords a standard reference condition.
The presence of nominal bicarbonate might effect the availability
of zinc in one of several or a combination of several ways.
Two
possibilities are increased solubility and increased rate of transfer
of zn+t from solution or Zn(OH) 2 to the inside of the root.
This study
does not attempt to separate these possible effects but is designed to
9
measure the crterall effect of nominal bicarbonate.
The approximate amounts of each of the three chemical species
(H2oo 3, HCOj, and ooj) that would be present under different conditions,
as calculated .from the well-known ionization constants, appear in
table 1.
10
Table 1 .
pH
6
7
8
Approximate amounts of H2co 3 , HCO j, and COj present under
different conditions of pH and nominal bicarbonate l evels
Nominal HOOj level
H2C03
Hco3
(~ ./liter)
(me ./liter)
c~ ./lite r )
co•
3
(me ./liter)
1
o . 70
0.30
1. 7
X
10 -5
3
2.10
0 . 90
5
X
10-5
6
4 . 20
1 . 80
X
10-4
1
0 . 19
0 . 81
5
X
10-4
3
0 . 56
2. 44
1. 4
X
10-3
6
1 . 12
4. 88
2. 8
X
10-3
1
0 . 024
0 . 98
5.6 x
lo- 3
3
0 . 072
2. 92
1 . 7 x lo- 2
6
0 . 140
5 . 83
3. 8 x lo-2
1.
11
EXPERIMENTAL ME'IHODS
Corn and tomato plants were selected to indicate uptake of zinc
from solution under varied conditions of bicarbonate concentrations.
'llle plants were grown in quartz sand and frequently irrigated with
the nutrient solution suggested by Hoagland and Arnon (19).
Tomatoes
were five to eight weeks old and corn three to five weeks old when
removed from the sand and used for the study .
During the zinc uptake period, the plants and experimental solutions were contained in 600 ml. Griffin beakers with aerating stones
inserted through their bottoms .
(See figure 1.)
A waxed cover
supported the plant and kept the solution from contamination.
The
small metal surface on the aerating stone was coated with inert tygon
paint, while the outside o! the beaker was painted with asphalt
aluminum paint.
A buffer system of KH2F04-NaOH was used to stabilize
pH
(Clark and
!llbs, 13) , but because of the confusion in the literature about the
effects of phosphate on zinc uptake it was necessary to make an evaluation of this effect first.
A barbital-HCl buffer system (Britton, 6)
was used as another method of controlling pH to make this evaluation.
'llle experimental solution contained a b.tffer 1 KCl where necessary
3 and Znff (3.6 ppm), with
redistilled water to make up a total volume of SOO ml. Short uptake
to maintain constant ionic strength, NaHco
periods were used to prevent the concentration of bicarbonate from
changing appreciably as the equilibrium concentration of carbon dioxide
er er:im.e ntal plan
-
vaxed cardboard
cove r
re.:i nted 600 ml._
Grif fin beiiker
Figure 1.
Cutavo.y diu -rwn c f exrerL"!.entJ.l urr...rst'lls
use d for the study of zinc ~v~ilability
vs. bicarbonate.
13
was not maintained over the solutions to prevent the equilibrium
reaction 2HCOj
¥ •
C02 • coj from shifting to the left or right.
Upta.ke periods of 6, 12, and 24 hours were used.
The pH determinations
of the solutions were taken at the beginning and end of each uptake
period.
Radioactive zinc (zn65) was used to facilitate the measurement of
zinc uptake in this experiment.
It was obtained from Oak Ridge Labora-
·~
tories of the Atomic Energy Commission and had been assayed by them to
be 99 per cent p.1re zn65cl2•
Working solutions •ere made by using a
dilution factor of 10:1 of stable ZnC12 to zn65cl2•
Radiation health
hazards were kept to a minimum by using proper methods of handling,
shielding, decontamination, and disposal (Lapp and Andrews, 23).
All reagents and solutions were made up with water that had been
redistilled from a pyrex distilling apparatus to prevent possible
zinc impurities in the water from changing the ratio of stable to
radio zinc.
When plants were harvested they were cut off
1t
inches above the
base of the s;tem, washed first in distilled water, then in
and finally in distilled water.
90° C. for 12 hours.
o.5 1:! HCl
They were then dried in an oven at
After drying, each whole upper portion of the
plant was pressed into a pellet ll.5 mm. in diameter.
The J:ellets
were weighed, placed in bottle crown planchets as suggested by Marcour
and Woolley (26), and counted, using a Nuclear, model D.
scintillation counter.
s.
1,
Because of corustant geometry and careful
positioning, the absorption correction for gamma radiation can be
neglected.
The amount of zinc present was calculated by comparing the
radiation in the samples with that from a standard sample, maldng a
decay correction unnecessary.
The determined aiOOunts of zinc were then
converted to parts per million of the dry plant material and this used
for evaluation.
15
RESULTS
Preliminaq experiments
A preliminary experiment was conducted to determine the effect of
the phosphate buffer system on the uptake of zinc from solution.
The
experimental solutions containing zn65 were placed in twelve adapted
beakers and maintained at six duplicate pH values between 6 . 3 and 8.3,
,/
one set being controlled with KH2P04-NaDH buffer system and the other
set with the barbital-HCl system.
Two of the selected pH values proved
to be beyond the ruf:fering range of the barbital-HCl system and the
remaining four of this set were somewhat higher than was anticipated.
Corn was used as the indicator plant and was a.llowed a. 24-hour uptake
period.
The information received from this experiment is presented in
figure 2 .
The uptake of zinc is plotted as a function of pH.
The
solid lines are the regression lines for the data obtained from the
two sets of buffered solutions.
The area between the dashed lines
represents the confidence interval of the phosphate line at the five
per cent level.
The fact that the barbital line is on the outside of
the confidence interval reveals that phosphate has a significant
retarding effect on the uptake of zinc by corn.
In both cases the
effect of pH appears to be linear.
Other preliminary expel'i!mnts were conducted using corn or
tomatoes to absorb zinc from solution.
It was found that the pH
values obtained, using phosphate buffer system, could not be predetermined with the accuracy necessary to allow the results to be
16
\
\
32
''
''
· -- - Barbital-HCl
\
\
\
.'
\
28
\
\
'\
\
'\
\
\
'
\
-e
\
\
\
\
\
'\
Q,
Q,
-
\
\
\
'
\
liJ
\
~
'
t!
C1.
::l
c
'\
'
''
'
''
\
\
'
\
'\
N
\
\
\
''
KHf0 4 -NaOH
'
'
\
\
'
\
''
\
\
8
'
6.6
\
\
'
\
'
\
'
\
7.4
PH
Figure 2. Regression lines rerresenting the data plotted of
zinc ur-take by corn in 2.4 hours as a furction cf '~"H vith
the pH being controled by tw systems; ;m2'o~, -~:c~Cn w:C.
b;...rbital-HCl ' uffers. T Je are:~. betwen the dashed lines
rerresents the confidence interval cf the Y"H{O - NaCH line
4
at the 5'1 level, sho'Wing a significant increase in the
uptake of zinc i _n the absence of r 11osrhate.
17
analyzed wi u, analysis of variance.
A graph ( fie:;ure 3) was also
obtained with zinc uptake plotted as a functi:m of ?ll at a constant
nominal (five milliequivalents per liter) bicarbonate level.
The
break in the straic;ht line relationshitJ of pH apparently results from
the presence of nom:Cnal bicarbonate.
The absorbing plants in this
case were tomtoes and were allowed a 24-hour uptake period.
Bicarbonate-~-plant relati~nship
Corn.
Twenty-four solutions buffered at six pH values with four
nominal HCO) levels at each
~!
were used to obtain valid
concerning the HCO)-Zn relationshi?•
info~.ation
The actual pH values obtained
varied sornew'·.at from the intended values.
Corn was used to absorb
zinc from these solutions, using a six-hour period.
The data for each nominal bicarbonate level were plotted wit:O zinc
uptake as a function of pH.
From these four ;;raphs a series of plots
(figure 4) were obtained with uptake as a fcmction of nominal bicarbonate concentration at a given pH.
These plots show that the uptake
of zinc increased with increasins bicarbonate, up to a characteristic
concentration, then it leveled off or was slightly reduced by further
increase in bicarbonate.
to the gener-.al trend.
The curve representing }JE G is an exce;;tion
It shows that tile uptake of zinc increased
with inc::-easin0 bicarbonate throutj1out the concentration range studied.
Tomatoes.
The experimental system for to:-.a toes was the same as that
used for com except that a 12-hour uptake period was used.
The data
obtained were analyzed in the same manne:r as for tl1e previous corn
experiment and the curves representing the uptake of zinc as a function
of nominal bicarbonate concentration at a given pE
a~pear
in
fi~re
:io satisfactory explanation is apparent to explain fully why zinc
5.
22
~
e
Q.
-
Q.
w
::.::
18
i!CL
:::>
0::
N
J4
e.s
PH
1
Fit(l:.re j.
line uptatce t,y tt:HnAL(·e3 ::_;t 12 _Jqrs as a :~· . . :::::t~.o-.,
of-·pE at a constant nominal '"'ic:rr·con-J\e level ( S ;r.e ./ L) ,
The break in t~'1e <:lJrve res~;Jt-i::~; ::_n greater npt2.ke at tLc l~er
nE value a is attributed tc ~J101inal bicar·co,atc.
""! '')
18 ...
~-~~---r-------.--.--:r--P-r-1H-6'1.
-;-r-
--~---r---1
~
16rPH
6.&
E
Q.
Q.
fJ H
7.0
PH 7.5
PH
_ _L ___L __ _L ___ L
I
Nomino4
/ie;-.;.rt:
4.
e.o
1.. __L ___ ___L_.L_____l__J_---!.--_.
5
[Hco;J Cme./tl
'·-'!Jt..U.c c:' z ir:c L~; coTJl ir: 0 :.....x l--.otir::i :1s a fu.nG t.lc·c L.:.f..
nor..inal bicarbonate concentration at a ,;iven ,;E.
E
0.
Q.
r:
N
~
I
3
Nominal
[Hco-J (me./U
6
Fi151;re S.
Uptake of zinc by tcrnatoes in 12 hours ~s a ft:nction
of nominal bicarbonate concentration at a r;i ven pll.
21
uptake should be affected by bicarbonate concentrations in this manner,
The curve at pH 8 for tomatoes is similar to the one obtained at pH 8
in the corn experiment• which may have some bearing on the uptake of
zinc by the two species,
Statistical ana1ysis,
A multiple regression analysis using the
mathematical model Y •
f
+C)'! pH 1' "1' 2pH2 •e\HCO)
•€ 2HCOj2 .. (5 3Hcoj3
was attempted in order to permit a test for significance of HCOj ion
independently of pH on the uptake of zinc by corn and tomatoes,
A
complete solution of this model was found to be impossible because
q2 approached zero.
After omitting the termq' 2pH 2 from the model 1 a
solution was obtained,
The analysis revealed that the effect of pH in both experiments
was linear and far exceeded significance at the one per cent level;
that the effect of HCOj nominal on the uptake of zinc by corn was not
significant; and that the curveleaner effect of nominal HCO) on the
uptake of zinc by tomatoes as reasured by
€2HCOf and €3Hcoj3 in the
mathematical model was significant at the five per cent level.
data and statistical analysis are given in the appendix.
The
22
DISCUSSION
The statistical analysis has shown the effect of nominal bicarbonate
on the uptake of zinc by com to be insignificant.
This fact is
probably traceable to variation resulting from an unwise choice in the
uptake period, because, for short uptake periods the uptake from
solution is roughly proportional to the root surface area which is
not usually uniform.
Witb a proper uptake period the effect of nominal
bicarbonate would probably have been si¢ficant.
seemed to be effected in the expected fashion.
The zinc uptake
The uptake of zinc was
increased with increasing nominal bicarbonate to a characteristic concentration.
It then leveled off or was slightly reduced, possibly by
a common ion effect.
It is doubtful that the concentration of nominal
bicarbonate was sufficient to restrict respiration.
The uptake of zinc by tomatoes as influenced by nominal bicarbonate
is not easily explained.
The plots of uptake vs. bicarbonate indicate
points of maximum and minil!D.lm, as does the significance of the higher
order interaction terms.
Just what would cause this type of inter-
action is at present undetermined.
The similarity in the plots of uptake vs. nominal bicarbonate at
pH 8 for both corn and tomatoes, and their difference from tile otber
plots, indicate that nominal HCOj' may not be as effective at the
higher pH values.
The information obtained indicates tbat under some conditions an
increase in uptake of zinc can result from the presence of nominal
23
bicarbonate.
There is, apparently, increased zinc availability under
the following conditions:
1.
Zinc deficiency symptoms seldom occur on poorly drained
soils (29).
2.
Zinc deficiency symptoms occur less frequently on the
heavier textured soils (42,
44).
3. Deep-rooted perennials feed on zinc from the lower soil
horizons (18 1
4.
41).
Zinc deficiency symptoms often disappear if intertilled
crops are grown in orchards (10).
One nrl.ght hypothesize that the increased zinc availability results from
higher concentra tions of nominal bicarbonate.
to the higher concentration of
This in blm is related
co 2 from poorer aerated conditions or
increased root activity.
While the primary purpose of this study was to determine the
effect of bicarbonate on zinc availability, some of the sideline information obtained is noteworthy.
A pH effect on the uptake of zinc has
been proven conclusively to exist.
'lhe existence of a linear pH
effect throughout mst of the so-ealled critical range and beyond
should cause us to
re~xamine
some of the material in the literature.
This critical range was found to exist by Lott (24), Camp (9) 1 and is
supported by the work of Jurinakl.
However, a real conflict may not
exist as their studies involved soils and this study did not.
The
existence of a critical range may result from a soil-zinc relationship.
Zincate formation was suggested by Camp (9) to exist above pH of
1.
Jurlnak, J.
soils. (M.
College.
J. 1954. 'lhe available forms of zinc in alkaline
s.
Thesis.
Dep t. of Agrononzy-)
Utah State Agricultural
24
7.85.
If zincate was formed it was not evidenced by increased uptake
in this study.
The reduction in uptake of zinc in the presence of phosphate has
here been demonstrated in an independent method.
the conclusions of many workers
tion to others
(5,
(4,
11, 12, 30,
22, 31}, notably Pearson.
This finding supports
45)
and is in opposi-
He states that phosphate
will reduce uptake of zinc only at >iJ values above 9.
He also states
that the reduction in zinc uptake, often noticed upon application of
phosphate to the soil, results· from the cat't associated witb such an
application.
The concentration of phosphate in this experiment
(H2P04 • HPOi; • 0.05
!!)
was very much higher than is ordinarily found
in soil solutions, and it may be that reduction in uptake of zinc will
be observed only at relatively high concentrations of phosphate, as
noted by Jamison (21).
The system and methods for this study are well adapted to determine
if the cat't-zn't't antagonism really exists, as hypothesized by Pearson2.
l.
Pearson, G. A.
1951.
Some factors influencin<; absorption of zinc
(,b. D. dissertation.)
University of California. Berkeley.
by roots from single salt solutions.
25
StnlMARY
1.
The purpose of this study was to determine the influence of bicarbonate on the uptake of zinc
2.
~
crops.
zn6S facilitated the measurement of the amounts of zinc taken from
solution by plants under varied conditions of pH and bicarbonate
concentrations.
3. Hlosphate was found to have a retarding effect on the uptake of
zinc by corn.
4.
The effect of pH on the uptake of zinc
found to be inverse-linear.
~
corn and tomatoes was
'Ibis effect far exceeded significance
at the 1 per cent level.
5.
The uptake of zinc by corn in the presence of nominal bicarbonate
was not found to differ significantly from uptake in the absence
of bicarbonate.
Vari.abili ty resulting from too short an uptake
period is the probable cause for lack of signif icant response.
6.
The curvelinear effect of nominal bicarbonate on the uptake of zinc
by tomatoes was significant at the S per cent level.
7. The uptake of zinc
by some crops can be favorably influenced
presence of nominal bicarbonate.
~
the
This may explain why deficienci es
are not found as frequently under poorly aerated conditi.ons as under
well-aerated conditions with other conditions being the same.
26
LITERATIJRE CITED
1.
Alben, A. o., and H. M. Boggs. 1936. Zinc content of soils in
relation to pecan rosette. Soil Sci. 41:329-353.
2.
Barnette, R. M. 1936. The occurance and behavior of the less
abundant elements in soils. Fla. Agr. Exp. Sta. Ann. Rpt. pp. 61.
3. Barnette, R., s. P. Camp, and J. D. Warner. 1 936. The use of
zinc sulfate under corn and other field crops.
Sta. Bul. 292.
Fla. Aer. Ex:p.
4.
Baumann, A. 1885. Das Verhalten von Zinksalzen ~Pflanzen
und in Boden. Die liiidW Verscuchstat 31:1-53. (Orieinal ref.
not seen. Cf. Jones' Gall and Barnette ( 22).)
5.
c., F. G. Viets , and C. L. Crawford. 1954. Effect of
phosx:hate fertilizers on zinc nutrition of field beans. Soil
Sci. 78:1-7.
6.
Britton, H. T. s. 1932. Hydrogen ions 2nd Ed.
Company, Inc. N. Y. pp. 220-234.
1.
Brown, A. L. 1950.
Sci. 69:349-358 .
B.
Camp, A. F. 1945. Zinc as a plant nutrient in plant growth .
Soil Sci. 60:154-157.
9.
Camp, A. F., and l'f. Reuther. 1937. Studies of the effects of
zinc and other unusual mineral supplements on the growth of
horticulture crops. Fla. Agr. Exp. Sta. Ann. Rpt. pp. 132-135.
Boawn, L.
D. Van Nostrand
Zinc relations in Aiken clay loam.
Soil
10.
Chandler, w. H. 1937.
Gaz. 98:625-646.
ll.
Chandler, w. H., and D. R. Hoagland, and P. L. Hibbard. 1933.
Little leaf or rosette of fruit trees III • .?roc. Amer. Hort.
Soc. 30:70-86.
12.
Chapman, H. D., A. P. Vanselow, and G. F. Liebig. 1937. The
production of citrus mottled leaf in controlled nutrient cultures.
Jour. Agr. Res. 55:365-379.
13.
Clark, W. M., and H. A. Lubs.
2:109-136.
14.
Elgabaly, U. Y. 1950 . Mechanism of zinc fixation by colloidal
clays and related minerals . Soil Sci. 69:167-174.
Zinc as a nutrient for plants.
1917.
Buffer solutions.
Bot.
J. Bact.
27
15.
Epstein, E., and P. R. Stout. 1951. The micronutrient cations
iron, manganese, zinc, and copper: their uptake by plants from
the absorbed state. Soil Sci. 72:47-64.
16.
Gall, 0. E. 1936.
Ind. 17: 20-21.
17. Hibbard, P. 1940.
Hilgardia 13:1-29.
Zinc sulfate studies in the soil.
Citrus
The chemical status of zinc in the soil.
18.
Hibbard, P. 1940. Accumulation of zinc in soils under long
persisted vegetation. Soil Sci. 50:53-55.
19.
Hoagland, D. R. 1 and D. I. Arnon. 1950. The water culture method
for growing plants without soU. Calif. Agr. Exp. Sta. Circ. 347.
20.
Hoagland, D. R., W. H. Chandler, and P. L. Hibbard. 1936. Littleleaf or rosette of fruit trees : V. Effect of zinc on the growth
of plants of various types in controlled soil and water cultural
experiments. Proc. Amer. Soc. Hort. Sci. 33:131-141.
21.
Jamison, V. C. 1943. The effect of phosf(lates upon the fixation
of zinc and copper in several Florida soils. Proc. Fla. State
Hort. Soc. 56:26-Jl.
22.
Jones, H. w., o. E. Gall, and R. M. Barnette. 1936. Reaction
of zinc sulfate with the soil. Fla. Agr. Expt. Sta. Bul. 298.
23.
Kruyt, H. R. 1952. Colloid Science Vol. 1. Irreversable
Systems .
Elsevier Publishing Co.
N. Y.
1948.
pp. 176.
24.
Lapp, R. E. 1 and H. L. Andrews.
Physics. Prentice-Hall. N. Y.
Nuclear Radiation
25.
Lott, w. L. 1938. The relation of hydrogen ion concentration
to availability of zinc in the soU. Soil Sci . Soc. Amer. Proc.
3:115-129.
26.
Marcour, M., and J. T. Woolley. 1951. Use of bottle crown
planchets in radio-tracer studies. Nucleonics 9:76.
27.
Yaz~, P.
1914. Influences respectives des elements de la
solution minerale sur le detvelopuent du mais . Inst. Pastuer
ltUi. 28:21-28. (Orlginal ref. not seen.---cf. Chandler (10).)
28.
Mellor, J. w. 1924. A comprehensive treatise on inorganic and
theoretical chemistry. Vol. 4. London: Longmans, Green and Co.
29.
Mowry, H., and A. F. Camp. 1934. A preliminary report on zinc
sulfate as a corrective for bronzing of tung trees. Fla. Agr.
Exp. Sta. Bul. 273.
30.
Newell, w., H. Mowry, and R. Barnette.
tree. Fla. Agr. Exp. Sta. Bul. 221.
1930.
The tung oil
28
31.
Peech, M. 1941. Availability of ions in light sandy soils as
affected by soil reaction. Soil Sci. 51:473-48o.
32.
Powers, w. L., and T. s. Pang. 1947. Status of zinc in relation
to soil fertility. SoU Sci. 64:29-36.
33. Rogers, L. H. 1946.
The role of zinc in crop production.
Citrus Ind. 27:9-12.
34.
Rogers, L. H., and Cheh-Hwa Wu. 1948. Zinc uptake by oats as
influenced by application of lime and phosphate. Am. Soc. Agron.
Jour. 40:563-566.
35.
Shaw, E., and L. A. Dean. 1952. Using dithizone as an extractant to estimate the zinc nutrient status of soils. Soil Sci.
73:341-347.
36.
Shawt~.,
37.
Sormner, A. L. 1928. Further evidence of the essential nature of
zinc for the growth of higher green plants . Plant Physiol. 3:217221.
38.
Sommer, A. L., and c. B. Lipman. 1926. Evidence of the indispensable nature of boron and zinc for higher plants. Plant
Physiol. 1:231-249.
39.
Staker, E. v. 1942. Progress report on the control of zinc
toxicity in peat soils. Soil Sci. Soc. Amer. Proc. 7:387-392.
40.
Staker, E. V., and R. W. Cunmings. 1941. The influence of zinc
on the productivity of certain New York soils. Soil Sci. Soc .
Amer. Proc. 6:207-214.
41.
Thorne, D. w., w. D. Law~, and A. Wallace. 1943.
ships in some Utah soils. Soil Sci. 54:463-468.
42.
Thorne, D.
and F. B. Wann •. 1950. Nutrient deficiencies in
Utah orchards. Utah Agr. Exp. Sta. Bul. 338.
43.
Truog, E. 1947. Soil reaction influence on availability of plant
nutrients. Soil Sci. Soc. Amer. Proc. 11:305-308.
R. G. Menzol, and L. A. Dean. 1954. Plant uptake of
zinc 0 5 from soils and fertilizers in the greenhouse. Soil Sci.
77:205-214.
Zinc relation-
w.,
44. Wann, F. B., and D. w. Thorne. 1950. Zinc deficiency in plants
in the Western States. Scientific Mon. 70:18o-l84.
h5. West, E. s . 1938. Zinc-cured mottled-leaf in citrus induced
excess phosphate.
182-184.
by
Jour. Council Sci. and Indus. Res. Aust. 11:
V • .J,.V
.L•.)f
0
29
APPENDIX
Data and Statistical Analysis
f or Uptake of Zinc by Corn in a Six-hour Uptake Period
Beaker No.
pH
Uptake
HCO-
ppm
me . /liter
2
1
6. 13
16. )4
0
2
5. 95
15. 41
1
3
6. 35
17. 93
3
4
6. 55
lh. 62
6
5
6.48
8. 64
0
6
6. 55
13.75
1
7
6. 70
10. 58
3
8
6. 89
12. 82
6
9
6. 89
12. 24
0
10
6.91
7. 49
1
11
7. 07
13.9.
3
12
7. 20
4. 97
6
13
7. 20
1.44
0
14
7. 30
4. 75
1
15
7.57
5. 83
3
16
7. 70
6. 91
6
17
7. 61
3. 67
0
18
7. 70
3. 02
1
19
8.01
1•.30
3
20
8. 10
1.37
6
30
Da ta and statis t i cal analysis , c ontinued .
pH
Beaker No .
HCO-
Uptake
3
ppm
me . / l i ter
21
7. 87
3. 0 2
0
22
7. 97
2.2)
1
23
8. 39
4 . 75
3
24
8. 45
2. 23
6
Multiple Regression Analysis type analysis
~
Mathemati cal Model: Y ::
f' +0( pH + ~ 1HC03
+
~2HC03
2
+ @3H003
3
Solved Mathematical Model:
~
Y • J.4h . 669000 - 17. 9Bol 35 pH + 1.8h8165 H003
• 211885 HOO 3 3
A. N. O.
D. F.
~ Sgs .
Total uncorrected
Total due to model
Residual
24
5 . 449079
5 . 110306
Mean
pH
HCO)
(HCOj) 2
(HCOj )3
*
Highly significant at l% level.
2
-
v.
Source
5
19
1
1
1
1
1
-+ . 117900 HC03
M S ~s .
. 017830
1 . 709745*
1 . 346o 7l*
. 001463
. 002621
. oo6CQ4
31
Data
and Stati stical Analysis
f or Uptake of Zinc b.y Tomatoes
in
a 12-bour Uptake Period
Beaker No .
pH
Uptake
ppm
HCO3
me . /liter
1
5. 68
8. 26
0
2
5. 87
9.h5
1
3
6. 20
7. 96
3
4
6. 48
6. 98
6
5
6.35
4.64
0
6
6.41
8. 81
1
7
6. (JJ
4. 34
3
8
6. 80
8. 24
6
9
6. 73
6.03
0
10
6. 83
5.18
1
11
7.10
3. 69
3
12
7. 18
2.83
6
13
7.21
4. 38
0
14
7.20
4.62
1
15
7.41
3.08
3
16
7. 61
2. 54
6
17
7.53
1. 72
0
18
7. (JJ
2. 80
1
19
7. 73
. 72
3
20
8. 21
1. 85
6
21
7. 70
1.13
0
22
7. 90
1.14
1
23
8. 19
1.01
3
24
8. 62
. 96
6
32
. rultiole Type stotistic., 1 ,n., lys i s
!at hem!l ticAl .'odel:
Solved
~:>them;> tic,
j)\ = /
«.. + ~ 1 oH
+11.ii2HC03 2
1
/)
1"/.r 3HC~
3
1 1'odel:
1\
jl=
+ 8 1HC~
28 , 671290 - 3 . 533180 pH
1"
2 . 094 566 HC~ - 1. 030150 HC~ 2
1"
, 121187 Hco 3
3
~.
u. o. v.
Source
D.F.
Total uncorrected
Tot~ l due to model
Residu.q,l
24
5
19
1
1
1
'e a.n
•
pH
HCO)
(HC03)2
( HCOj)3
*
S ignific ~nt
1
1
.qt the
5~
leve l,
f Sos .
t~
Sos •
6 .160336
5. 917774
. 012766
1.9405 50
l. L4M~82
o.
51863
0 . 056069~~
0 , 060660*