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Journal of Plant Nutrition

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The chemistry of iron in

soils and its availability to
plants
a a
W.L. Lindsay & A.P. Schwab
a
Department of Agronomy, Colorado State
University, Fort Collins, Colorado, 80523
Published online: 21 Nov 2008.

To cite this article: W.L. Lindsay & A.P. Schwab (1982): The chemistry of iron in
soils and its availability to plants, Journal of Plant Nutrition, 5:4-7, 821-840

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X. BEHAVIOR OF IRON IN SOILS

 JOURNAL OF PLANT NUTRITION, 5 ( 4 - 7 ) , 8 2 1 - 8 4 0 (1982)

THE CHEMISTRY OF IRON IN SOILS AND ITS

AVAILABILITY TO PLANTS

Keywords
Iron d e f i c i e n c y , r e d u c t i o n , c h e l a t i o n , a b s o r p t i o n , s o l u b i l i t y , and
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critical nutrient l e v e l .

W.L. Lindsay and A . P . Schwab

Department o f Agronomy
Colorado S t a t e U n i v e r s i t y
Fort C o l l i n s , Colorado 80523

ABSTRACT
The s o l u b i l i t y o f i r o n i n s o i l s i s c o n t r o l l e d by F e ( 0 H ) 3 ( s o i l ) i n
w e l l - o x i d i z e d s o i l s , by F e 3 ( 0 H ) s ( f e r r o s i c hydroxide) in m o d e r a t e l y
o x i d i z e d s o i l s , and by F e C 0 3 ( s i d e r i t e ) i n h i g h l y reduced s o i l s . The
F e ( I I I ) h y d r o l y s i s s p e c i e s Fe(OH) 2 + , and Fe(OH)3° a r e t h e major s o -
l u t i o n s p e c i e s o f i n o r g a n i c F e , but t h e y a r e maintained t o o low t o
supply a v a i l a b l e i r o n t o p l a n t s . Iron i s absorbed by p l a n t s a s F e 2 +
and must be i n t h e general range > 1 0 - 7 . 7 M t o avoid i r o n d e f i c i e n c y .
The redox o f s o i l - r o o t environments must be <12 t o supply adequate
F e 2 + f o r p l a n t s . Hawkeye soybeans ( G l y c i n e max. L. M e r r i l l ) demon-
s t r a t e d t h e a b i l i t y t o reduce t h e i r environment t o pe + pH 4 t o 7 by
r e l e a s e o f e l e c t r o n s o r o t h e r r e d u c t a n t s i n t o t h e r o o t medium. Re-
d u c t i o n by p l a n t r o o t s and a s s o c i a t e d microorganism i s an important
mechanism f o r s o l u b i l i z i n g F e 2 + .

Iron c h e l a t e s a i d i n t h e movement o f i r o n t o p l a n t r o o t s , but

t h e y a r e n e i t h e r absorbed t o any g r e a t e x t e n t nor do t h e y r a i s e t h e
a c t i v i t y o f F e 3 + o r F e 2 + i n t h e bulk s o i l s o l u t i o n . To be e f f e c t i v e
iron c h e l a t e s must be s t a b l e i n s o i l e n v i r o n m e n t s . Chemical e q u i l -
ibrium r e l a t i o n s h i p s a r e u s e f u l i n p r e d i c t i n g i r o n s o l u b i l i t y and
a v a i l a b i l i t y in s o i l s .

821

Copyright © 1982 by Marcel Dekker, Inc.

 822 LINDSAY AND SCHWAB

INTRODUCTION

Calcium carbonate buffers s o i l s in the general pH range of 7.4

to 8.5. In t h i s pH range iron oxides a t t a i n t h e i r minimum solu-
b i l i t y , and iron deficiency i n plants i s most severe. Many hypo-
theses have been advanced to explain the cause of iron deficiencies
and to account f o r the many factors associated with " i r o n chlorosis"
(Thorne et a l . , 1951). Hopefully t h i s conference w i l l help to
focus attention on the problems of i r o n n u t r i t i o n and pinpoint the
areas where f u r t h e r research is needed.

The objectives of t h i s paper are to examine the basic chemical

reactions which control iron s o l u b i l i t y i n s o i l s and show how these
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reactions control the a v a i l a b i l i t y of iron to p l a n t s . To accomplish

these objectives i t is necessary to recognize the iron minerals that
occur in s o i l s , the speciation of iron in s o i l s o l u t i o n , the effects
of redox and pH on iron s o l u b i l i t y , the s t a b i l i t y and role of metal
chelates in iron n u t r i t i o n , and how a l l of these factors i n t e r a c t to
determine the a v a i l a b i l i t y of iron to p l a n t s .

SOLUBILITY OF FERRIC OXIDES

The dissolution and p r e c i p i t a t i o n of f e r r i c oxides is the major

factor controlling the solubility of iron in soils. The activity of
Fe^"1" maintained by these oxides is highly pH dependent as shown in
Fig. 1. The solubility of Fe3+ decreases 1000-fold for each unit
increase in pH and is depressed to levels below 10"^ H as pH rises
above 7.5. The Fe(III) oxides shown here have different s o l u b i l i -
ties which decrease in the order Fe(OH)o(amorp.)>Fe2(OH)3(soil )>Fe2O3
(maghemite)>Fe00H(lepidocrocite)>Fe203(hematite)>Fe00H(goethite).
These oxides span a solubility range of 10 3 ' 5 6 or 3630-fold. Thus
freshly precipitated 4-day old Fe(0H)3(amorp) is 3630 times more sol-
ubile than goethite. Norvell and Lindsay (1982) showed that iron
solubility in well-aerated soils tends to approach that of Fe(0H)3
(soil) or Soil-Fe as i t is designated. Its solubility is represented
by the reaction.

Fe(0H)3(soil) + 3H+ $ Fe3+ + 3H20 log K° = 2.70 (1)

I f soluble iron salts are added to well-aerated soils, they

quickly dissolve to precipitate Fe(0H)3(amorp). Over a period of
several weeks the solubility of iron decreases slowly and approaches
that of Soii-Fe. We view Soil-Fe as an amorphous Fe(III) oxide that
has stabilized to some extent and is several fold less soluble than
the f i r s t precipitated material. Since Soil-Fe establishes equilib-
rium f a i r l y quickly, i t plays a very important role in controlling
the solubility of iron in well-aerated soils.
 THE CHEMISTRY OF IRON IN SOILS 823

• Fe(OH)3 (amorp)

Fe(OH)3 (Soil-Fe)

(maghemite)

•y-FeOOH (lepidocrocite)
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-22 - a-FeOOH (goethite)

Fig. 1 (left). The activity of Fe 3 + in equilibrium with various

Fe(III) oxides (from Lindsay, 1979).

Since the level of Fe^ + maintained by Soil-Fe is greater than

that maintained by crystalline Fe(III') oxides, these crystalline
minerals can theoretically precipitate and lower Fe3+ to their equi-
librium levels. The precipitation of crystalline Fe(III) oxides,
however, occurs very slowly. Schwertmann and Taylor (1977) discus-
sed the conditions believed to be necessary for the formation of the
various iron minerals. The presence of crystalline iron oxides in
soils is no guarantee that iron solubility is controlled by them.
Only the most readily dissolvable form that is present controls iron
solubility. It is for this reason that Soil-Fe is so very important
in soils. Only very old soils (oxisols) not subject to frequent
changes in redox or intensive microbiological activity are expected
to accumulate large quantities of crystalline iron oxides which may
eventually control iron solubility.
 824 LINDSAY AND SCHWAB

HYDROLYSIS AND COMPLEXATION OF FE(III)

Ferric ions hydrolyze readily in aqueous media to give a series

of hydrolysis products. Figure 2 shows how the various hydrolysis
species change with pH when F e 3 + is controlled by Soil-Fe. The pre-
dominant solution species is Fe(0H)2+ below pH 7.4, FeCOH)?0 between
pH 7.4 and 8.5, and Fe(0H)4~ at higher pH. The minimum solubility
of iron is attained in the pH range of 7.4 to 8.5 and is fixed at
10-10.4M when equilibrium is established with Soil-Fe.

-4r-
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-6

-8

-10

£ -12

-16

-18

-20

-22
6
PH

Fig. 2 (right). The hydrolysis species of Fe3+ in equilibrium with

soil-Fe (Lindsay, 1979).
 THE CHEMISTRY OF IRON IN SOILS 825

If Fe(III) oxides less soluble than Soil-Fe control Fe 3 + solu-

bility, then the lines in Fig. 2 representing hydrolysis species
would shift down accordingly, but the slopes of the lines would re-
main the same (Lindsay, 1979). Thus Fig. 2 can be used to obtain
the solubility limits of Fe 3 + activity.
Ferric iron also forms complexes with other anions in solution
It is important to know if such complexes can increase iron solubil-
ity above that permitted by the hydrolysis species. Many of the
common inorganic complexes of Fe(III) are plotted in Fig. 3. The
inorganic complexes shown here are insignificant compared to the
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-4r

-22

Fig. 3 ( l e f t ) . Complexes of Fe(III) in equilibrium with soil-Fe in

comparison to the hydrolysis species (Lindsay, 1981).
 826 LINDSAY AND SCHWAB

hydrolysis species. Thus the solubility of inorganic iron in well-

aerated soils is determined solely by the hydrolysis species and
the solid phases governing Fe3 + activity.
Not represented in Fig. 3 are the natural organic matter com-
plexes of iron which are present in soil solution. The presence
of such complexes raises total iron in solution and adds to its total
solubility, mobility, and availability to plants (Lindsay, 1974).
Such complexes need further study and characterization. The exuda-
tion of organic acids or other complexing agents by plants or other
organisms in the root zone undoubtedly play an important role in
increasing total iron solubility in soils.
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EFFECT OF REDOX ON IRON SOLUBILITY

The redox relationships of iron in soils are such that both
Fe(III) and Fe(II) are important. The equilibrium reaction relating
these two oxidation states is given by:
Fe 3 + + e" t Fe 2 + log K° = 13.04 (2)
This relationship can be rearranged to give

£
FeJ
o 13 - 04 " pe
io13-04" pe
(3)

where pe is the negative log of electron activity (e~). For those

who are more familiar with Eh as a redox parameter, the following
conversion is useful:
Eh(mv) = 59.2 pe (4)
o I Ox
According to Eq. 3 when pe = 13.04 the ratio+ of Fe /Fe is unity.
For each unit decrease in pe, the ratio Fe2 /Fe3+ in solution in-
creases 10-fold.
As redox is lowered,
+
some point will be reached where the
activities of Fe^ and its hydrolysis species will exceed those of
Fe^ + . These conditions are depicted in Fig. 4. At pe + pH 20.6,
which represents equilibrium with atmospheric oxygen, the activit-
ies of Fe(III) hydrolysis species greatly exceed those of Fe(II).
As pe + pH of most soils tends to approach 7.0 as they are reduced,
these two ions are the predominant iron species in solution. Thus
reduction does not increase the solubility of iron appreciably
until pe + pH drops below 12.0. One of the major benefits of 2 +
flooding rice soils is to reduce the soil sufficiently that Fe
becomes available to plants. Reduction is of little benefit until
the pe + pH drops below 12.
 THE CHEMISTRY OF IRON IN SOILS 827

-2

-4

-6-

-8

6-IO
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-12

-14-

-16

Fe(HD
-18
-—FeOD

-20
4 5 6 7 8 9
PH

Fig. 4 (right). The effect of redox of Fe 2 + and FeOH + in comparison

to Fe(III) hydrolysis species in equilibrium with soil-Fe.

Let us consider the solubility relationships of iron from a

slightly different perspective. Depicted in Fig. 5 is a plot of
log Fe2+ activity maintained by various iron minerals as a function
of redox. The activity of Fe 2 + in equilibrium with Fe(III) minerals
increases 10-fold for each unit decrease in pe + pH. For mixed
valency minerals like Fe304 (magnetite) and Fe3(0H)g(ferrosic hyd-
roxide) there is a 2/3 log Fe 2 + increase since only 2/3 of the iron
is these minerals is present as Fe(III); the other 1/3 is already
present as Fe(II). At the very low redox, iron solubility is con-
trolled by FeC03(siderite). Since the iron in this mineral is pre-
sent as Fe(II), redox does not affect its solubility when expressed
in terms of Fe2+ , However, the solubility of siderite is lowered
one log unit for each unit increase in log COp(g). Although
Fe(0H)2(C) is often mentioned in the literature as a possible iron
 828 LINDSAY AND SCHWAB

pH
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8 10 12 14 16 18

Fig. 5. The effect of redox on the

activity of Fe? + maintained by
various iron minerals.

mineral in reduced soils, Lindsay (1979) has shown that to be vir-

tually impossible.
The solubility relationships in Fig. 5 are drawn for pH 7.0.
The graph can be used for other pH values by noting that the lines
shift upward 2 log units for each unit decrease in pH and downward
for a similar increase in pH. Thus Fig. 5 can be used to estimate
the activity of Fe 2 + supported by any of the minerals shown thereon
as a function of redox, pH, and C02(g). Many of the iron minerals
represented in Fig. 5 may be present in soils and yet not control
the solubility of iron; only the most readily equilibrated phase
will do that.
Schwab and Lindsay 1982a) examined the solubility relationships
of iron reported in the literature for soils and other natural
environments. Only those measurements that included redox and pH
could be used. Their findings are summarized in Fig. 6 and are
discussed below.
 THE CHEMISTRY OF IRON IN SOILS 829

LEGEND
O Back & Barnes, 1965
X Barnes & Back. 1964

Got
Heli & Slnex, 1974
• Ungmulr 6 Vhittemore, 1971
isrlcha & Ponnamperuma, 1976
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8 10 12 14 16 18

Fig. 6. Solid phase control of iron solubility

under different redox conditions summarized
from the literature (Schwab and Lindsay, 1982a).

Back and Barnes (1965) measured iron conentrations in ground

waters. Many of the Fe 2 + activities computed from their data fell
near the Fe3(0H)g(ferrosic hydroxide) line while others fell near
siderite, magnetite, or amorphous ferric hydroxide. Barnes and Back
(1964) reported similar findings for ground waters in Maryland.
Doyle (1968) examined synthetic solutions of ferrous sulfate
subjected to different pH and redox conditions. Most of his data
points fell near the amorphous ferric hydroxide line. Gotoh and
Patrick (1974) made similar measurements butatlower redox. Their
solubility points fell near the FeC03(siderite) line. Since no CO2
measurements were made, an exact interpretation of their data is
not possible.
Iron solubility measurements of thermal springs in Virginia
(Helz and Sinex, 1974) reflects the presence of Fe,(OH)g(ferrosic
hydorxide). Langmuir and Whittemore (1971) examined ground waters
in New Jersey and their results tend to cluster near Fe(0H)3(soil),
magnetite, goethite, or possibly siderite. By means of mineral
analysis they confirmed the presence of lepidocrocite and goethite
in some of their samples.
 830 LINDSAY AND SCHWAB

Pasricha and Ponnamperuma (1976) and Ponnamperuma et al. (1967)

measured iron solubilities in submerged soils at high bicarbonate
levels. There solubility points fall near the ferrosic hydroxide
and siderite lines.
The results reported in Fig. 6 certainly indicate that iron
solubility relationships tend to reflect equilibrium with various
recognized solid phase iron compounds when pH, redox, C02» and
appropriate ion pair corrections are made. By knowing the solid
phases which govern iron solubility, it is then possible to predict
Fe 2 + activity as a function of pH, redox, and CO2.
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Schwab and Lindsay (1982a) measured iron solubility, pH, redox,

sulfate, C02(g), ionic strength, and other parameters of soil sus-
pensions maintained in carefully controlled redox cells. Their
results are plotted in Fig. 7 and show that iron solubility was
controlled by FeCC>3(siderite) below pe + pH 8 and by Fe3(0H)8(fer-
rosic hydroxide) in the pe + pH range of 8 to 16. Apparently these
two solid phases are important in establishing the solubility re-

8 . 10 18
pe*pH
Fig. 7. Evidence that FeC03(siderite) controls
iron solubility below pe + pH 8 and that Fe3(0H)g
(ferrosic hydroxide) controls i t at higher redox
from 8 to 16 (Schwab and Lindsay, 1982a).
 THE CHEMISTRY OF IRON IN SOILS 831

lationships of iron in highly reduced and moderately reduced soils,

respectively.
It was surprising to us at first that FeofOHjoCferrosic hydr-
oxide) played such a dominant role in controlling iron solubility
in these studies, especially under redox conditions where even
amorphous ferric hydroxide could precipitate. We hypothesize that
reduced microsites exist in soil suspensions near respiring plant
roots or microorgranisms. Since redox was controlled in our sus-
pensions by occasionally admitting small amounts of a gas mixture
containing 94% N2, 5% CO2, and \% O2, the equilibrating soil solution
may have become temporarily more oxidized than the microsities near
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2+
plant roots and respiring organisms. As a result, Fe formed in
the reduced microsites and combined with Fe^ + formed in the oxidized
soil solution and precipitated the mixed valency Fe3(0H)8(ferrosic
hydroxide).
Further studies are needed to examine this hypothesis and to
determine how long the metastable ferrosic hydroxide persists. The
studies reported have indicated that it can persist for several
weeks. According to the above hypothesis, fluctuating redox condi-
tions at microsites in soils could favor the formation and persis-
tence of this metastable form of iron hydroxide.

CRITICAL LEVELS OF IRON FOR PLANTS

Knowing that iron solubility in soils is controlled by solid
phases in soils, how can we relate iron in solution to the availa-
bility of iron to plants? Schwab and Lindsay (1982b) attempted to
examine these relationships for soybeans (Glycine max. L. Merrill).
Their findings are replotted in Fig. 8 in terms which are conven-
ient for the discussion that follows.
In their study 59p e uptake was measured from a nutrient
solution over a 24-hour period. Iron was added as 5 p|1 FeDTPA
(diethylenetriaminepentaacetic acid), and the concentration of
free Fe 2 + was controlled by adding excess levels of various che-
lates agents including DTPA, CDTA (cyciohexane-1, 2-diaminetetra-
acetic acid), or BPDS (bathophenanthroline disulphonic acid). 2A+
computer program was developed to calculate the activity of Fe in
these solutions (Schwab and Lindsay, 1982c). The measured uptake
rates over a 24-hour period were integrated over the 21 days of
growth to give the average ppm level of iron that would be accumu-
lated by soybean plants.
2+
Iron uptake was linearly related to Fe in solution above2 +
9#z
10" H. Below this level, iron uptake was independent of Fe
and appeared to reflect a low-level absorption of the chelated form
of iron. This low rate of iron uptake amounted to 6 nmol/g/day and
would provide only 9 ppm of Fe in the plants. The important con-
 832 LINDSAY AND SCHWAB

90P
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log Fe 2 +
Fig. 8. The relationship between Fe 2 +
in solution and the uptake of iron by
chlorotic Hawkeye soybeans. Based on a
24-hour uptake of 5 9 Fe and integrated
over a 21-day growth period (Schwab and
Lindsay, 1982b).

elusion from the data reported in Fig. 8 is that to supply plants

with 50 ppm Fe it would require 10"?.7^ Fe 2 + in the nutrient medium.
Plant species may differ in their ability to absorb iron, and other
factors may affect the development of iron chlorosis but the results
show that for soybeans grown under iron-stress conditions, Fe2+ must
be somewhere near 10"7#'f1 to avoid iron deficiency. Soils which
depress Fe^ + much below this level, can be expected to produce iron
deficienct plants.

The relatiohsips depicted in Fig. 8 are indeed exciting. First,

it appears that Fe 2 + is the solution species of iron that is most
 THE CHEMISTRY OF IRON IN SOILS 833

likely absorbed, and its concentration determines iron availability

to plants. Thus reduction plays a very important role in the up-
take of iron. The findings of Brown and Ambler (1973) and Cheney
et al. (1972) that reduction by root exudates is an important
mechanism for iron uptake is certainly supporting evidence. We
further found that iron-stressed plants released greater quantities
of reductants to the nutrient media than non-stressed plants
(Schwab and Lindsay, 1982b). We were able to show that the redox
near stressed plant roots may drop'as low as pe + pH 4 to 7. In
this redox range reductive processes certainly are important in
making iron available to plants.
If plants require approximately 107-7f1 Fe 2 + to be able to meet
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their nutritional needs, then it should be possible to estimate

the redox or pH conditions needed to prevent iron deficiencies.
Let us consider a soil with pH 7.0 in which Soil-Fe is controlling
iron solubility. From Fig. 5 it can be seen that pe + pH would
have to be<9.0 to provide >10 7 » 7 M Fe 2 + . On the other hand, if the
solubility of iron were controlled by Fe3(0H)8(ferrosic hydroxide),
the pe + pH would only have to be < 12.0 to avoid iron deficiency.
The importance of pH on Fe^ + solubility can also be illust-
rated from Fig. 5. The lines in Fig. 5 shift upward 2 log units
for each unit decrease in pH. A change in pH from 7.0 to 6.0 when
Soil-Fe controls iron solubility would require that redox only drop
•to 11.0 instead of 9.0, and when ferrosic hydroxyide is present to
14.0 instead of 12 to give 107«7t4 Fe 2 + , The importance of pH and
redox in controlling iron solubility and availability to plants is
obvious. Although lO" 7 - 7 ^ Fe 2 + is given here as the critical level
below which iron deficiency may occur, the actual critical level may
differ depending on plant species, reductive capacity of the roots,
acidifying effects of roots, the presence of chelating agents or
other factors.
ROLE OF CHELATING AGENTS IN IRON NUTRITION
For more than three decades synthetic chelates have been used
to correct iron dificiency in many crops (Wallace, 1962). Much of
our early knowledge of iron chelates was developed empirically. In
the mid 1960's theoretical developments were made to predict equi-
librium relationships of metal chelates in soils (Lindsay et al.
1967; Lindsay and Norvell, 1969). Later Norvell extended the theo-
retical approach to include other chelating agents and metal ions
(Norvell, 1972). Much recently developments have been made to pre-
dict the effect of redox on the displacement of metal ions from
chelating agents (Sommers and Lindsay, 1979; Lindsay, 1979). Many
of these theoretical relationships have been tested in soils and
found to be useful in predicting metal chelate reactions.
The usefulness of synthetic chelates to maintain soluble iron
in soils is illustrated in Fig. 9. As pH increases, F e 3 + i s de-
 834 LINDSAY AND SCHWAB

100
EDDHA^

EGTA\
I \ \
• I
EDTA\ 1
LJ 60
• DTPA

\
O \WcDTA
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O \ \I
20

7 10
PH
Fig. 9. The ability of various synthetic iron chelates to maintain
iron in solution as a function of pH.

pressed by formation of insoluble oxides (Fig. 1) causing iron to be

displaced from the chelates by divalent metal ions. Since Ca2+ is
maintained fairly constant in slightly acid to neutral soils by
cation exchange reactions (Lindsay, 1979), Ca2+ plays a dominant
role in displacing iron from chelating agents.
The ability of chelating agents to maintain chelated iron in
solution as pH rises increases in the order: EDTA<EDTA<DTPA<CDTA<
EDDHA (ethylenediamine di(o-hydroxyphenylacetic acid). Iron is dis-
placed from EGTA (ethyleneglycolbis(ethylamine)tetraacetic acid)
above pH 5.5, from EDTA (ethylenediaminetetraacetic acid) above pH
6.7, and from DTPA and CDTA above pH 7.7.
In general plants reflect the predicted behavior of various metal
chelates to supply iron. This is illustrated in Fig. 10 for the
chelates EDTA, DTPA, and EDDHA in a calcareous soil of pH 8.1. As
shown here, EDDHA provided the best correction of iron deficiency for
both first and second crops, reflecting its greater stability
at pH 8.1 for the soil used in this study.

For the first crop FeEDTA and FeDTPA provided more available
iron than might have been predicted, reflecting the fact that it
took time for iron to be displaced from these chelates (Norvell
and Lindsay 1969; 1972). By the second crop, however, the equili-
bria had more nearly been reached. FeEDTA was no longer able to
 THE CHEMISTRY OF IRON IN SOILS 835

CROP 1 CROP 2

1 16 I LSD 5% iLSD&Vo
O ''TeEDDHA
Q.
FeEDDHi
/

FeEDTA FeDTPA/
/
34
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UJ / x ^ XFeEDTA
0 2 4 6 8 0 2 4 6 8
Fe ADDED, ppm Fe ADDED, ppm

Fig. 10. The ability of various iron chelates to correct iron

deficiency in two successive sorghum crops (Lindsay, 1974).

provide available iron, and FeDTPA supplied only a small amount.

Thus plants reflect the predicted stability of iron chelates in
soils when account is taken of the fact that displacement of iron
from the chelates may require several weeks.

• When soils are reduced, metal chelates behave somewhat dif-

ferent than in well-aerated soils. Reduction of soils changes the
activities of several metal ions which compete for the chelating
ligands. An example of such changes is illustrated in Fig. 11,
which represents the theoretical stability relationships of EDTA in
a soil of pH 7.0 and 0.1 atm of CO?. Chelated M n 2 + increases
rapidly as reduction occurs, and displaces some of all the other
metal ions from the chelate. This displacement occurs around pe +
pH 16.5. At pe + pH 12, additional displacement of iron occurs
reflecting the fact magnetite rather than Soil-Fe is the mineral
fixing iron solubility. Had the diagram been drawn to include
Fe3(0H)s(ferrosic hydroxide) below pe + pH 16 as shown to be im-
portant in the studies discussed earlier, more iron would have been
present on the chelate. As pe + pH drops below 4, the Fe(II)
species become the major chelated fractions and are able to dis-
place some of the other metal ions that normally occupy the che-
lating agent. Experimental studies of the stability of EDTA and
DTPA in submerged soils have been reported (Reddy and Patrick, 1981;
1977). In general their observations support the predicted rela-
tionships discussed here.
 836 LINDSAY AND SCHWAB
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_ CUHL-/ / \ ^C \ MgH
/ / S^~ V \ \ HL'-

Fig. 11. Effect of redox on the equilibrium relationships of EDTA

in soils at pH 7.0 and C02(g) at 0.1 atm (Lindsay, 1979).

HOW CHELATES FUNCTION IN PLANT NUTRITION

Lindsay (1974; 1979) has pointed out that chelates do not in-*
crease the activity of Fe 3 + or Fe 2 + in soils; they only increase
the concentration of chelated iron. Chelated iron is important,
however, because it establishes a larger diffusion gradient to aid
in the transport of iron to plant roots. The method by which
chelates aid in the diffusion of iron to roots is shown diagram-
matically in Fig. 12.
Depicted in this diagram is a root hair that is separated by
a short distance from soil containing Soil-Fe. Chelated iron is
free to diffuse throughout the root medium and the apparent free
space of the root. It dissociates 3 +to maintain equilibrium with
free chelating ligand (L^-) and Fe tn solution. Also equilibrium
tends to be maintained between Fe 3 + and Fe 2 + according + to Eq. 2.
At the root surface both electrons (e-) and protons (H ) are re-
leased through plant respiration processes. Normally these com-
ponents are combined with oxygen to form water. Since the surface
of roots are generally more reduced than the bulk solution, the
Fe' + /Fe 3+ is greater and iron is more readily absorbed by plant
roots (Fig. 8 ) . Removal of Fe 2 + by the root also lowers Fe 3 + and
 THE CHEMISTRY OF IRON IN SOILS 837

Root
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Fig. 12. A diagrammatical representation showing chelation,

diffusion, reduction and absorption function in the vicinity of
plant roots to aid in the uptake of iron.

causes the iron chelates (FeL~) to dissociate releasing free ligand

(L 4 ~). The absorption process establishes a diffusion gradient of
FeL" toward the root and L^~ away from the root.
The driving force that enables chelating agents
+
to function in
the vicinity of plant roots is the release of H and e- and the up-
take of Fe 2 + . The rate limiting step of diffusion is overcome by
the presence of chelated iron which is generally added at levels of
10-6 or 10—5_M[ compared to 10-10-4JM Fe(0H)3O which is the most
abundant inorganic Fe(III) species in well-aerated soils in the pH
range above 7.4 where iron deficiences most often occur (Fig. 2 ) .
The presence of excess chelating agent in nutrient solutions
can retard and even inhibit the uptake of iron by plants (Brown
et al., 1960; Chaney et al., 1972; Schwab and Lindsay, 1982b).
This competition occurs in nutrient solutions where excess chelating
is either added or accumulates and no additional solid phase Fe(0H) 3
is present to provide additional Fe 3 + to combine with the excess
chelating agent. In soils the problem of excess chelating agent
does not occur because there is always 3ample Fe(0H)3 present to
resaturate the chelating agent with Fe + .

CONCLUSIONS
1. Iron deficiences in plants are most prevalent in alkaline soils
where the solubility of iron is depressed by the formation of
insoluble ferric oxides.
 838 LINDSAY AND SCHWAB

2. A stabilized amorphous ferric oxide referred to as Soil-Fe most

likely controls iron solubility in well oxidized soils. Soil-
Fe is less soluble than freshly precipitated iron oxide but more
soluble than the common crystalline forms of ferric oxide.
3. Iron solubility in slightly reduced soils can be controlled by
Fe3(OH)o(ferrosic hydroxide) which comprises both ferric and
ferrous iron. This compound is more soluble than amorphous
ferric oxide,and an hypothesis is proposed to account for its
formation in partially reduced soils.
4. In highly reduced soils iron solubility is apparently controlled
by 2 FeC03(siderite). Increasing CO2 depresses the solubility of
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Fe + maintained by this mineral, but the presence of siderite

would assure adequate available iron for plants.
5. Evidence indicates that absorption
2+
of iron by plants is directly
related to the activity of Fe in the nutrient media. A crit-
ical level of 10"7-7iM Fe 2 + is needed in the nutrient medium for
chlorotic soybeans to absorb sufficient iron to provide plants
with 50 ppm of iron over a 21-day growth period.
6. Plants have the ability to reduce the environment around roots
to very low levels. For example, chlorotic Hawkeye soybeans
reduced their growth medium to pe + pH of 4 to 7. This reduct-
ive mechanism may vary among plant species but it plays an
important role in solubilizing iron and making it available for
absorption.
7. Chemical equilibrium relationships are useful in predicting the
effects of pH and redox on the solubility and availability of
iron to plants. For example, in a soil of pH 7 in which Soil-
Fe controls iron solubility, pe + pH must be lowered to 9 to
supply adequate Fe 2 + for absorption. If Fe3(0H)o is present,
pe + pH could be as high as 12. If the pH were 6 instead of 7,
the required redoxes would be 11 and 14, respectively.
8. Chelating agents are only beneficial in increasing iron availa-
bility to plants if they are sufficiently stable to retain iron
in chemical environment of soils. Stability constants can be
used to predict their stability.
9. Chelating agents do not increase the activity of Fe 3 + or Fe
in soils but they increase the concentration of chelated iron.
Chelated iron diffuses to the root where the chelate dissociates,
Fe 3 + is reduced to Fe 2 + and Fe 2 + is absorbed by root. The che-
lating agent diffuses away to become resaturated with iron from
the soil.
10. Chemical equilibrium relationships in the soil-plant root
environment ultimately control the solubility of iron and its
availability to plants.
 THE CHEMISTRY OF IRON IN SOILS 839

ACKNOWLEDGMENTS
Published as Colorado State University Scientific Series No.
2691. Appreciation is extended to Tennessee Valley Authority for
support through Cooperative Agreement No. 1131-101.

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