The Nature and Properties of Soils (9-10)

,
-..
.. , ~
~
~.
[Preceding page] Soil-borne bacteria in the root nodule of this soybean plant illustrate
a symbiosis which is responsible for the biological fixation of enormous quantities of
nitrogen. {Courtesy Ray R. Weil, University of Maryland. College Park. MD.]
Of the various essential elements. nitrogen probably has been subjected to

the most study and still receives much attention. And there are very good
reasons. The amount of this element in available forms in the soil is small.
while the quantity withdrawn annually by crops is comparatively large. At
times. there is too much nitrogen in readily soluble ' forms, and it is lost in
drainage, and may even become a water pollutant; at other times, it is lost
from the soil by volatilization; at all times, most of the soil nitrogen is unavail-
able to higher plants. Moreover, its effects on plants usually are very marked
and rapid. Thus over application, which may be harmful, sometimes occurs.
Some plants, such as the legumes, have associated with their roots soil
organisms that "fix" atmospheric nitrogen into forms that they can use. Others,
such as the grasses, are largely dependent upon outside sources-either through
nonsymbiotic fixation or through the addition of fertilizers or other combined
forms of nitrogen. All in all, nitrogen is a potent nutrient element that should
be not only conserved but carefully regulated.
9.1 Influence of Nitrogen on Plant Development

Favorable Effects. Nitrogen is an integral component of many compounds
essential for plant growth processes including chlorophyll and many enzymes.
It is an essential component of the proteins and related amino acids, which
are critical not only as building blocks for plant tissue but in the cell nuclei
and protoplasm in which the hereditary control is vested. It is essential for
carbohydrate utilization within plants and stimulates root growth and develop-
ment as well as the uptake of other nutrients. Of the macronutrients usually
applied in commercial fertilizers, nitrogen seems to have the quickest and
most pronounced effect. It encourages aboveground vegetative growth and im-
parts deep green color to the leaves. With cereals, it increases the plumpne_ss
of the grain and the percentage of protein. With all plants, nitrogen is a regulator
that governs to a considerable degree the utilization of potassium, phosphorus,
and other constituents. Moreover, its application tends to produce succulence,
a quality particularly desirable in such crops as lettuce and radishes.
Plants receiving insufficient nitrogen are stunted in growth and possess
restricted root systems. The leaves tum yellow or yellowish green ana-tend
to drop off. The addition of available nitrogen will cause a remarkable change,
indicative of the unusual activity of this element within the plant.
Oversupply. When higher applications of nitrogen than necessary are made,

the leaves become dark green in color and excess vegetative growth occurs.
As a result, the stems are not able to hold the plants upright and they lodge
284 9 Nitrogen and Sulfur Economy of Soils

or fall over with the slightest wind. Also, crop maturity is delayed and the
plants are more susceptible to diseases and insect pests. An oversupply of
nitrogen may adversely affect grain and fruit quality, as in barley, apples,
and peaches. It also adversely affects sugar levels in sugar cane or sugar beets.
It must not be inferred, however, that all plants are detrimentally affected
by large amounts of nitrogen. Many crops, such as the grasses and vegetables,
should have plenty of this element for their best and most normal development.
Detrimental effects are not to be expected with such crops unless exceedingly
large quantities of nitrogen are applied. Nitrogenous fertilizers may be used
freely in such cases, the cost of the materials in respect to the value of the
crop increases being the major consideration.
9.2 Forms of Soil Nitrogen

There are three major forms of nitrogen in mineral soils: (a) Erganic nitrogen
associated with the soil humus, .(b) ammonium nitrogen fixed by certain clay
m inerals, and (c) soluble inorganic ammonium and nitrate compounds.
Most of the nitrogen in surface soils is associated with the organic matter.
In this form it is protected from rapid microbial release, only 2-3% a year
being mineralized under normal conditions. About half the organic nitrogen
is in the form of amino compounds. The form of the remainder is uncertain.
Some of the clay minerals (e.g., vermiculites and some smectites) have
the ability to fix ammonium nitrogen between their crystal units. The amount
fixed varies depending on the nature and amount of clay present. Up to 8%
of the total nitrogen in surfa~e soils and 40% of that in subsoils may be in
the "clay-fixed" form. In most cases, however, both these figures would be
considerably lower. Even so, the nitrogen so fixed is only slowly available
to plants and microorganisms.
The amount of nitrogen in the form of solubl onium and nitrate com-
poundS is seldom more than 1-2% of the total present, except where larg~
applications of inorganic nitrogen fertiliZers liave oeen made. This is fortunate
Since inorganic nitrogen is subject to loss from soils by leachlng and volati~iza
lion. Only enough is needed to supply the daily requirements of the growing
crops.
9.3 The Nitrogen eyelet

In all soils the considerable intake and loss of nitrogen in the course of a
year are accompanied by many complex transformations. Some of these
changes may be controlled more or less by man, whereas others are beyond
I For this and subsequent sections on nitrogen. the reader is referred 10 the monograph ediled
by Stevenson (1982).
9.3 The Nitrogen Cycle 285

Animals Humans
Gaseous losses
e
~
~
N fixation
/~
I
~ ~ Losses
N2 .,;r E
N20 NH3 <
(rain) (fertilizer)
Residues,
manures,
and wastes
FIGURE 9.1 Main portions of the nitrogen cycle. Chemical fertilizers from industrial
nitrogen fixation are an increasingly important source of this element.
. .
his command. This interlocking succession of largely biochemical reactioris
constitutes what is known as the njtrogen cyCle (Figure 9.1). It has attracted
scientific study for years. and its practical significance is beyond question.
The nitrogen income of arable soils is derived from such materials as
commercial fertilizers. crop residues; green and farm manures. and ammonium
artanfuate salts brought down by preclPitatiOii':"In addition. trum~ is flle fixati~
of atmospheric nitrogen accomplished by certain microorganisms. The deple-
tion is due to crop removal, drainage. erosion; and to loss in a gaseous form.
. . Much of the nitrogen added to the soil undergoes many transformations
before it is removed. The nitrogen in organic combination is subjected to espe-

FIGURE 9.2 Two major pools of
soil nitrogen, their primary sources
and process es of transfer.
Organic
nitrogen
pool ....n~'
\mmobiliza=tio
Inorganic
nitrogen pool
(NH 4 + + N0 3 -)
position
cially complex changes. Proteins are converted into various decom
Even
products, and finally some of the nitrogen appear s in the nitrate form.
rest since it is either approp riated by microo rganism s
then it is allowed no
so the
and higher plants, removed in drainage, or lost by volatilization. And
on and on. The mobili ty of nitroge n is remark able, rivaling
cyclic transfe r goes
carbon in its ease of movement.
bulk of
Major Divisions of the Nitrogen Cycle. At anyon e time, the great
combin ations protec ted from loss but largely
the nitrogen in a soil is in organic
this reason much scienti fic effort has been
unavailable to higher plants. For
en-how it is stabiliz ed and how it may
devoted to the study of organic nitrog
plants. The p'roces s of tying-y p nitroge n in
be release d to forms usable by
n; its slow release -specif ically, organic
organic forms is called immobilizatio
to inorganic conversion-~alleJiglinera lization (Figure 9.2).
9.4 Immo bilization and Mine raliza tion

residues,
During the process of microbial decomposition of plant and animal
inorgan ic nitroge n as well as that
especially those low in nitrogen. the plant
Section 8.15) 'primar ily as microb ial
in the soil is converted to organic forms (see
es, some of this immob ilized
tissue. As the rate of microbial activity subsid
appear
nitrogen will be mineralized and ammonium and nitrate ions will again
immob ilized nitroge n remain s in the
in the solution. However. most of the
organic form.
to or-
The mechanism by which simple nitrogen compounds are changed
9.4 Immobilization and Mineralization 287

ganic combinations that resist breakd own is still obscure (see Section
8.10).
Somehow the immobilized nitrogen in the microbial tissue becomes an
integral
part of the soil organic matter. In this form it is only slowly minera
lized to
compounds usable by higher plants.
~al1y tagged nitrogen experiments have demon
strated that only
about 2-3%o rthe immob ruzed nitrogen is mineralized annually. Even
-----~~~~-=~~~~ so, -is
release of nitrogen to inorganic forms nas long supplied a significant portion
of crop needs and may be about 60 kg/ha of nitrogen per year for a represe
nta-
tive mineral surface soil.
. Although the general term mineralization covers a whole series of
reac-
tions, the net effect can be rather simply visualized. Heterogenous soil
organ-
isms, both plant and animal, attack the organic nitrogen compounds.
As a
result of enzymatic digestion, the more complex proteins and allied compo
unds
are simplified and hydrolyzed. The end product is ammonia. The enzym
atic
process may be indicated as follows, using an amino compound as an
example
of the nitrogen source.
enzymati c
R-NH2 + HOH hydrolysis
I R-OH + NH3 + energy
Amino
combinat ion
Mineralization seems to proceed to the best advantage in well-drained

aerated soils with plenty of basic cations present. It will take place
to some
extent under almost any conditions, however, becaus e of the great
number
of different organisms capabl e of accomplishing such a change. This
is one
of the advant ages of a general-purpose flora and fauna.
9.5 Utilization of Ammonium Compounds

The fate of the ammonium nitrogen (as shown in Figure 9.1) is fourfol
d. First,
considerable amounts are approp riated by organisms capabl e of using
this
type of compound, for example, mycorrhizal fungi (see Section 7.8) undoub
tedly
are able to absorb ammoniacal nitrogen and pass it on in some form
to their
host.
Second, higher plants are able to use this form of nitrogeri, often
very
readily. Young plants of almost all kinds are especially capabl e in this
respect,
although they seem to grow better if some nitrate nitrogen is also
available.
Azaleas, laurel, and other plants requiring low-lime soil are additio
nal exam-
ples. Still other plants, such as blueberries and some lowlan d rices, even
prefer
ammonium nitrogen to the nitrate.
Third, ammonium ions are subject to fixation by vermiculite and
to a
certain extent by some smectites and organic matter. In this fixed
form, the
nitrogen is not subject to rapid oxidation. although in time it may become
available. This will receive attention in the next section.
Finally. when plant and animal syntheses temporarily are satisfied. the
remaining ammonium nitrogen may go in a third direction. It is readily oxidized
by certain special purpose forms of bacteria. which use it not only as a source
of nitrogen but also as a source of energy. Thus. a much discussed and per-
haps comparatively overemphasized phase of biochemistry-nitrification-is
reached. It is so named because its end product is nitrate nitrogen. and it
will receive attention following a consideration of ammonia fixation.
9.6 Ammonia Fixation

Both the organic and inorganic soil fractions have the ability to bind or "fix"
ammonia in forms relatively unavailable to higher plants or even microorgan-
isms. Since different mechanisms and compounds are involved in these two
types of fixation. they will be considered separately.
Fixation by Clay Minerals. Several clay minerals with a 2:1-type structure

have the capacity to "fix" ammonium and potassium ions. Vermiculite has
the greatest capacity. followed by the smectites.
It will be remembered that these minerals have internal negative charges
that attract cations to internal surfaces between crystal units (see Section
5.6). Most cations that satisfy these charges can move freely into and out of
the crystal. In other words. they are exchangeable. Ammonium and potassium
ions. however. are apparently just the right size to fit into the "cavities" between
crystal units. thereby becoming fixed as a rigid part of the crystal (see Figure
10.16). They prevent the normal expansion of the crystal and in turn are held
in a nonexchangeable form. from which they are only slowly released to higher
plants and microorganisms. The relationship of the various forms of ammonium
might be represented as follows.
NH. + ;:= NIl.+ ;:= NH. +

(80il 80lution) (exchangeable) (fixed)
Ammonium fixation by clay minerals is generally greater in subsoils than

in topsoil because of the higher clay content of subsoils (Table 9.1). In some
cases this fixation may be considered to be an advantage since it is a means
of conserving soil nitrogen. In others. the rate of release of the fixed ammonium
is too slow to be of much practical value.
Fixation by Organic Matter. Anhydrous ammonia or other fertilizers that con-

tain free ammonia or that form it when added to the soil can react with soil
organic matter to form compounds that resist decomposition. In this sense
the ammonia can be said to be "fixed" by the organic matter. The exact mecha-
9.8 Ammonia Fixation 289

TABLE 9.1 Percentage of Total Nitrogen Fixed as NH.+ Ion in Clay Minerals at
Different Depths in Three Trinidad Soilsa
These soils had significant levels of 2: 1-type clays that are able to fix large quantities
of NH.+ ion.
Soil depth Fixed Nil. + nitrogen

Soil Composition of clay fraction (em) a8 "" of total N
Maracas Mica, kaolinite, geothlte (}-10 28.5

1Q.-30 43.4
5(}-70 72.9
McBean illite, kaolinite, Iron oxides (}-10 24.2
IG-30 33.2
5(}-70 88.9
Tarouba Montmorillonite (}-10 18.9
IG-30 48.1
5(}-70 63.5
• From Dalal (1977).
nism by which the fixation occur is not known, although reactions with phenols
and quinones as well as with carbohydrates are suspected (Nommik and Vah-
tras, 1981). The reaction takes place most readily in the presence of oxygen
and at high pH values.
The practical significance of organic fixation depends upon the circum-
stances. In organic soils with a high fixing capacity it could be serious and
would dictate the use of fertilizers other than those which supply free ammonia.
In normal practice on mineral soils, however, organic fixation should not be
too disadvantageous. In the first place, the fertilizers is often banded, thereby
contacting a relatively small portion of the entire soil mass and minimizing
opportunities for fixation. Furthermore, the fixed ammonia is subject to subse-
quent slow release by mineralization.
9.7 Nitrification
Nitrification is a process of enzymatic oxidation of ammonia to nitrates brought
about by certain microorganisms in the soil. It takes place in two coordinated
steps. The first step is the production of nitrite ions by one group of organisms
apparently followed immediately by their oxidation to the nitrate form by
another. The enzymatic oxidation is represented very simply as follows.
NH.+
Ammonium Hydroxylamine
--2H (0)
Y.z HONNOH ------ N0 2 -
Hyponitrite Nitrite
+ H+ + energy
1(0)
N0 3 - + energy
Nitrate

Under most conditions favoring the two reactions. the second transforma-
tion is thought to follow the first so closely as to prevent any great accumulation
of the nitrite. This is fortunate since this ion in any concentration is toxic to
higher plants. In very alkaline soils or where large fertilizer ammonia applica-
tions have been made. there is some evidence that the second reaction may
be delayed until after the ammonium ion concentration is reduced to a relatively
low level. This may result in nitrite accumulation of sufficient magnitude to
have an adverse effect on plant growth or to encourage gaseous losses of
nitrogen (see Section 9.10).
Organisms Concerned. Although some heterotrophic bacteria. fungi. and acti-

nomycetes are able to convert ammonia to nitrites. the bulk of this oxidation
is aue to a group of autotrophic bacterla1ncluding NjkQsomonas, NitrosoJobus,
and !fjJ.£o8..o§Pira. Organisms responsible for the oxidation of nitrites to nitrates
arer"the autotrophic bacteria. Nitrobacter. In common usage these groups are
referred to as nitrite and nitrate organisms.
Rate of Nitrification. Under ideal temperature. soil. and moisture conditions.

nitrification occurs at a ve~ rapid rate. especiaUywhere adequate ammonium
ion is available. Under ide;J" conal tions the nitrifying organisms can supply
nitrates at a rate that more than meets the needs of crop plants and may
result in excess nitrates. some of which are lost in drainage or by volatilization
(see Section 9.9).
9.8 Soil Conditions Affecting Nitrification

The nitrifying bacteria are quite sensitive to their environment. much more
so than most heterotrophic organisms. Consequently. soil conditions that influ-
ence the vigor of nitrification deserve practical consideration. They are (a) a
presence of adequate ammonium ion for oxidation. (b) aeration. (c) temperature.
(d) moisture. (e) active lime, (f) fertilizer salts. (g) the carbon/nitrogen ratio.
and (h) pesticides.
Ammonia Level. Nitrication can take place only if there is a source of ammo-
nia to be oxidized. Factors such as a high C/N ratio of residues, which prevents
the release of ammonia, also prevent nitrification. However, if the ammonia
is present at too high a level, it constrains nitrification. Heavy localized applica-
tions to alkaline soils of anhydrous ammonia fertilizer or urea, which by hydro-
lysis forms ammonia. appear to be toxic to Nitrobacter, resulting in the accumu-
lation of toxic levels of nitrite. Obviously, the level of ammonia is an important
regulator of nitrification.
Aeration. Since nitrification is a process of oxidation, any practice that in-

creases the soil aeration should, up to a point, encourage it. Plowing and culti-
9.8 SoU Conditions AlJecting Nitrification 291

vation. especially if granulation is not impaired. are recognized means of pro-
moting nitrification. Rates of nitrification are generally somewhat slower under
minimum tillage than where plowing and cultivation are practiced:
Temperature. The temperature most favorable for the process of nitrification

is from 27 to 32°C (80-90°F). In temperate regions the process proceeds slowly
at temperatures slightly above freezing and increases until the optimum tem-
perature is reached. Nitrification declines at higher temperatures. and essen-
tially ceases at temperatures above 50°C (122°F). The lateness with which
nitrification attains its full vigor in the spring is well known. application of
fertilizer nitrogen being used to offset the delay.
Moisture. Nitrification is markedly influenced by soil water content. the pro-

cess being retarded by both very low and very high moisture conditions. In
practice. it is safe to assume that the optimum moisture as recognized for
higher plants is also optimum for nitrification. One reservation must be made.
however. Nitrification will progress appreciably at soil moisture contents at
or even below the wilting coefficient.
Exchangeable Bases and pH. Nitrification proceeds most rapidly where there
is an abundance of exchangeable bases. This accounts in part for the weak
nitrification in acid mineral soils and the seeming sensitiveness of the organisms
to a low pH. However. within reasonable limits. acidity itself seems to have
little influence on nitrification when adequate bases are present. This is espe-
cially true of peat soils. Even at pH values below 5 these soils may show
remarkable accumulations of nitrates (see Section 14.8).
Fertilizers. Small amounts of many kinds of salts. even those of the trace
elements. stimulate nitrification. A reasonable balance of nitrogen. phosphorus.
and potassium has been found to be helpful. Apparently. the stimulation of
the organisms is much the same as is that of higher plants.
Applications of large quantities of ammonium nitrogen to strongly alkaline
soils have been found to depress the second step in the nitrification reaction.
Apparently the ammonia is toxic to the Nitrobacter under these conditions
but does not affect adversely the Nitrosomonas. Consequently. nitrite accumu-
lation may occur in soils very high in pH. Similarly. on such soils adverse
effects may result from a compound such as urea. which supplies ammonium
ions in the soil by hydrolysis.
Carbon/Nitrogen Ratio. The significance of the carbon/nitrogen ratio has been

rather fully considered (Section 8.14). so the explanation here may be brief.
When microbes decompose plant and animal residues with high C/N ratios.
they incorporate into their bodies all the inorganic nitrogen. It is thereby immo-
bilized. Nitrification is thus more or less at a standstill because of a lack of
ammoniacal nitrogen. this also having been swept up by the general purpose
292 9 Nitrogen and Sulfur Economy of sons

decay organisms. A serious competition with higher plants for nitrogen is
thereby initiated.
After the carbonaceous matter has partially decomposed so that emerging
material is no longer abundant and the C/N ratio of the remaining residue
reduced, some of the immobilized nitrogen will be mineralized and ammonium
compounds will again appear in the soil. Conditions are now favorable for
nitrification and nitrates may again accumulate. Thus, the carbon/nitrogen
ratio, through its selective influence on soil microorganisms, exerts a powerful
control on nitrification and the presence of nitrate nitrogen in the soil (see
Figure 8.5).
Pesticides. Nitrifying organisms are quite sensitive to some pesticides. If

added at high rates many of these chemicals essentially exhibit nitrification
whereas others slow the process down. Most studies suggest, however, that
at ordinary field rates the majority of the pesticides have only minimal effects
on the process. This subject is covered in greater detail in Chapter 20.
9.9 Fate of Nitrate Nitrogen

The nitrate nitrogen of the soil, whether added in fertilizers or formed by
nitrification, may go in four directions (Figure 9.1). It may (a) Q.e incorporated
into microorganisms, (b) be assimilated into higher plants, (c) be lost in drain-
~ ana Cd) ~p..~..fr~e nitrogen cyc e in a gaseous condition.
Use by Soil Organisms and Plants. Both plants and soil microorganisms read-
ily assimilate nitrate nitrogen. However, if microbes have a ready food supply
(for example, carbonaceous organic residues) they utilize the nitrates more
rapidly than do higher plants. Thus, the higher plants have only what is left
by the microorganisms and must await for the subsequent release of the nitro-
gen when microbial activity slows down (see Section 8.15). This is one of
the reasons crops often are able during a growing season to recover only
about half the fertilizer nitrogen added. Fortunately, some of the immobilized
nitrogen is released during the following growing seasons.
Leaching and Gaseous Loss. Negatively charged nitrates are not absorbed
by the negatively charged colloids that dominate most soils. Consequently,
nitrates are subject to ready leaching from the soil, moving downward freely
with the water. The amount of nitrate nitrogen lost in drainage water depends
upon the climate and cultural conditions; it is low in unirrigated arid and
semiarid regions and high in humid areas and where irrigation is practiced.
Heavy nitrogen fertilization, especially for vegetables and other cash crops
grown on coarse-textured soils, accentuates loss by thiS'means. In recent years,
widespread use of high levels of nitrogen fertilizers applied broadcast before
the crop is planted has increased nitrate leaching losses. Coupled with concen-
9.9 Fate of Nitrate Nitrogen 293

trated losses from huge feedlots in some areas of the midwest and the great
plains states, the nitrates in drainage water in a few areas may have increased
to levels that could be harmful to humans and other animals. The need to
take steps to minimize these losses is obvious. This subject is given further
consideration in Section 20.11.
Gaseous loss of nitrogen from soils may occur in several forms. Perhaps
the most important is through denitrification whereby nitrates are reduced to
nitrogen oxide compounds and to elemental nitrogen. This process may be
carried out by soil microorganisms or through purely chemical reactions. In
alkaline soils ammonia gas may also be lost to the atmosphere in significant
quantities. These loss mechanisms will each be discussed briefly.
9.10 Denitrification
Nitrates are subject to reduction in soils, especially in those that are poorly
drained and low in aeration. The process is known as denitrification. Among
the reduction products are nitrogen gases, which can be lost into the atmo-
sphere. The nitrate reduction is due primarily to microbial action, although
some chemical reduction occurs.
Reduction by Organisms. The reduction of nitrate nitrogen to gaseous com-

pounds is the most widespread type of volatilization. Biochemical reduction
is most common. The microorganisms involved are common facultative anaero-
bic forms. They prefer elemental oxygen but under inadequate aeration can
use the combined oxygen in nitrates and some of their reduced products. The
exact mechanisms by which the reductions take place are not known. However,
the general trend of the reactions may be represented as follows.
-2 [OJ -2 [OJ - [OJ -[OJ

2 N0 3- --- 2 N02- - - - 2NO - - - N20 - - - N2
Nitrates Nitrites Nitric Nitrous Elemental
oxide oxide nitro8en
Each step in the reaction is triggered by a specific reductase enzyme.

Thus, nitrate reductase, nitrite reductase, nitric oxide reductase, and nitrous
oxide reductase all appear to be involved. It should be emphasized, however,
that the reaction can stop at any stage and the gaseous products released
(Figure 9.3).
Under field conditions, nitrous oxide and elemental nitrogen are lost in
largest quantities, N2 0 dominating if ample N0 2 - is present and if the soil is
not too low in oxygen (Figure 9.4). Nitric oxide loss is generally not great
and apparently occurs most readily under acid conditions.
It should be noted that N20 can be formed in small quantities by certain
Nitrosomonas bacteria during ammonia oxidation in aerobic soils. While this

Soil surface
,,+-t-- -part esca~es as gas~
,..... .~. - ... - • J '
&6 N0 3 -
~
0 =0
0 =N
Nitrate
- Nitrite - Nitric oxide -
.
Nitrous oxide - Nitrogen gas
FIGURE 9.3 Illustration of the reductive nature of the denitrification process loses
leave the nitrite ion. which in tum
ms take an oxygen from nitrate and
Organis
(1980); used with
an oxygen and produc es nitric oxide. and so on. [Modified from Hughes
permiss ion of Deere & Compa ny. Moline. IL.]
practical
obselVation is of some scientific interest. it is not thought to be of much
importance.
nitrogen
Chemical Reduction. There are nonmicrobial processes by which
For instanc e. nitrites in a slightly
may be reduce d in soils to gaseous forms.
when brough t in contac t with certain
acid solution will evolve gaseous nitrogen
unds such as urea, and even with
ammonium salts, with simple amino compo
followi ng reactio n sugges ts what may
lignins, phenols, and carbohydrates. The
happen to urea.
2 HNOz + CO(NHz)2 - CO 2 + 3 H20 + 2 Nz T

Nitrite Urea
either
This type of gaseous loss is strictly chemical and does not require
e soil conditi ons. Its practic al impor-
the presen ce of microorganisms or advers
tance, however, is not too great.
n is
Quantity of Nitrogen Lost Through Denitrification. Since gaseous nitroge
in this form is serious . As might be
unavai lable to higher plants, any loss
losses will depend upon the cultura l
expected, the exact magnitude of the
region soils that are not too heavily
and soil conditions. In well-drained humid-
g. Where
fertilized, the gaseous losses are probab ly less than those from leachin
large applica tions of ammon ia and urea ferti-
drainage is restricted, and where
9.10 Denitrification 295

80
,
70 /"
Elemental nitrogen (N 2 ) ----1
60
~
E 50
'"'"
.2
...c
0lI Nitrous oxide (N 2 0)
40
.~c
'"
;j
0
~
'" 30
<..:l
20
10
o 2 4 6 8 10 12 14 16 18
Time (days)
FIGURE 9.4 Denitrification 108S of three nitrogen gases fron an anaerobic acid Norfolk
sandy loam at 12.5% moisture. A closed system was used. Apparently N2 was wrmed
from the reduction of N20. Under field conditions much of the N20 would probably
have gone off as a gas and would not have remained to produce elemental N2. [From
Cady and Bartholomew (1960).]
lizer are made. substantial losses might be expected. 20-40% of nitrogen added
not being too uncommon.
In flooded soils such as those used for rice culture. losses by denitrification
may be very high. Often 60-70% of the applied fertilizer nitrogen is volatilized
as oxides of nitrogen or elemental nitrogen. The reason for this high loss is
simple. Ammonium-containing fertilizers added to or near the soil surface are
oxidized to nitrates in the thin oxidized layer just below the soil-water inter-
face. The nitrates then move down the profile into the reduced soil zone below.
which is very low in oxygen (Figure 9.5). Denitrification then occurs and losses
as N2 and N2 0 take place. Luckily this loss can be cut back by incorporating

Oxygen
diffusion
Floodwater
2-10 em
Aerobic layer
<2 em
--
-NH, TO'"
+ - - Nitrification-
.- "T. .
-: . ·
-=--=-- -
"o...:--=-~
Diffusion Oif·fusion
0.216 cm 2 /day 1.33 cm~ /day
Anaerobic
layer
>2cm
NH.Log"
n 1.
Nitrate nitrogen N2
O,g,mk "'''''''" • ~';t;"":::.)

. . N2 0
FIGURE 9.5 Nitrification-denitrification reaction and kinetics of the related processes

controlling nitrogen loss from the aerobic-anaerobic layer of a flooded soil system.
Nitrates. which form in the thin aerobic soil layer just below the soil-water interface.
diffuse into the anaerobic (reduced) soil layer below and are denitrified to the N z and
N20 gaseous forms, which are lost to the atmosphere. Placing the urea or ammonium-
containing fertilizers in the anaerobic layer greatly reduces the 108s. [From Patrick
and Reddy (1977); used with permission of the Japanese Society of Soil Science and Plant
Nutrition.}
the fertilizer into the reduced zone, thereby largely preventing the formation
of nitrates by nitrification. In some cases fertilizer use efficiency has been
doubled by deep placement of the fertilizer.
Atmospheric pollution. The loss of nitrous oxide (NzO) from the soil into
the atmosphere is thought to have some deleterious effects on the environment.
As the NzO moves up into the stratosphere, it may participate in reactions
that result in the destruction of ozone (0 3 ), a gas that helps shield the earth
from harmful ultraviolet radiation from the sun. If this ozone shield were to
be removed, the earth's surface would be warmed and serious ecological conse-
quences then would result. While the validity of this hypothesis is still being
evaluated, it suggests that NzO loss from soils may have implications far beyond
agriculture.
9.10 Denitrification 297

9.11 Nitrification Inhibitors 2
Losses of nitrogen by volatilization as well as by leaching are generally higher
when considerable nitrate nitrogen is present in the soil over long periods of
time. Such losses are high when nitrogen fertilizers are applied in the fall for
the succeeding crop or even in the spring on wet soils. To minimize them, it
is desirable to keep much of the applied nitrogen in the ammonium rather
than the nitra te form.
In recent years chemicals have been found that can inhibit the nitrification
process. Several such chemicals have shown promise under controlled condi-
tions (Table 9.2), but field performance has been spotty. One of the more effec-
tive of these chemicals is nitrapyrin [2-chloro-6-(trichloromethyl)pyridine] sold
under the brand name ofN-Serve. The compound inhibits oxidation of ammonia
to nitrates. It is relatively inexpensive and can be applied at rates of 0.5 kg/
ha or less. It is usually applied with anhydrous ammonia or incorporated into
dry fertilizer such as urea.
TABLE 9.2 Examples of Inhibitors of Nitrification-
Common name or symbol Chemical name
Dd. DNDN. Dicyan Dicyandiamide

Thiourea, Tu Thiourea
ASU Guanylthiourea
Nitrapyrin, N-Serve 2-Chloro-6-( trichloromethy I) pyridine
ST Sulfathiazole
MAST 2-Amino-4-methyl-6-trichloromethyl-1,3,5-triazine
ATC 4-Amino-1,2,4-triazole' HCl
• From Hauck (1980).
Response to nitrapyrin is variable and depends to a considerable extent

on the soil texture and the time of year the nitrapyrin and the fertilizer are
applied (Table 9.3). Poorest results are obtained with coarse-textured soils
and best with those higher in clay. Reduction in nitrogen loss from the use
of nitrapyrin is least when the fertilizer is placed on the soil surface alongside
growing plants.
Sulfur-Coated Urea. Another means of reducing gaseous loss of nitrogen is

by coating urea pellets with elemental sulfur. These sulfur-coated urea products
have been found to be effective in increasing plant utilization of the nitrogen,
especially on sandy soils and on some tropical soils, including rice paddies.
The sulfur is strictly not a nitrification inhibitor but it slows down the rate
of conversion of urea to ammonia and of ammonia to nitrates, thereby reducing
2 For reviews of this subject, see ASA (1980).

TABLE 9.3 Probability of Crop Yield Increases· from
Nitrification Inhibitors Applied with Ammonical Fertiliz-
ers at Different Times of the Year in the Eastern Part of
the Midwestb
Tune of application
Spring Spring
Soil texture Fall preplant sidedreaa
Sanda Poor Fair Fair

Loamy sands. sandy
loams, and loams Fair-good Fair Poor
Silt loams Good Fair Poor
Clay loams and clays Good Good Poor
• Chance of increase at any location any year, Poor =

<20%; Fair = 20-60%; Good = >60%.
b Nelson and Huber (1980).
the availability of nitrates for the denitrification process. Unfortunately, how-

ever, the sulfur adds significantly to the cost of the urea fertilizer (25-50%).
Also, it increases soil acidity, since oxidation of the sulfur in the soil produces
sulfuric acid (see Section 9.27). These compounds will likely be economical
only where high yield increases are obtained and/or where high crop values
prevail.
9.12 Ammonia Volatilization

Application of ammonium-containing fertilizers or of urea, which quickly hydro-
lyzes to ammonia, can result in significant losses of ammonia gas, especially
on sandy soils and on alkaline or calcareous soils. In upland soils this loss
is most serious when the urea or ammonium-containing materials are applied
to the soil surface. Not only are the opportunities for the ammonia to react
with soil colloids minimized with surface applications, but surface soil tempera-
tures are usually high, which enhances ammonia volatilization. Incorporating
the fertilizers into the top few centimeters of soil can reduce ammonia loss
by 25-75% over levels found when the materials are applied on the surface.
Gaseous ammonia loss from nitrogen fertilizers applied to the surface of
paddy soils can be appreciable even on slightly acid soils. The applied fertilizer
stimulates algae growing in the paddy water, which in turn can extract CO 2
from the water just as higher plants extract this gas from the atmosphere.
The result is a marked increase in paddy water pH, levels above 9.0 not being
uncommon. At these pH values ammonia is released from ammonium com-
pounds and goes directly into the atmosphere. As with upland soils, this loss
can be reduced significantly if the fertilizer is placed below the soil surface.
9.12 Ammonia Volatilization 299

9.13 Biological Nitrogen Fixation
For centuries farmers have recognized that the yields of cereal crops such as
wheat and com (maize) are higher when these crops are grown after certain
legumes such as clovers, and alfalfa (lucerne). We now know this beneficial
effect is due not to the legume crop itself but to associated microorganisms
that are able to fix atmospheric nitrogen into combined forms usable by the
plants. This ability to fix atmospheric nitrogen is known to be shared by a
number of organisms including several species of bacteria (not all of which
are associated with legumes), a few actinomycetes and blue-green algae (cyano-
bacteria). The quantity of nitrogen fixed globally each year is enormous, having
been estimated at about 175 million Mg (metric tons) (Table 9.4), which exceeds
the amount applied in chemical fertilizers.
The Mechanism. Although biological nitrogen fixation is accomplished by a

number of organisms, a common mechanism for the fixation appears to be
involved. The overall effect of the process is to reduce nitrogen gas to amonia,
~
~
(nitrogenase)
N2 + 6 H+ + 6 e- , 2 NHa
TABLE 9.4 Biological Nitrogen Fixation from Different Sources-
Nitrogen fixed per year
Area Rate Total fixed

Ule (1(11 ha) (kg/ha) (1(11 Mg)
Arable (cropped)
Legumes 250 140 35
Nonlegumes 1,150 8 9
Permanent meadows and grassland 3,000 15 45
Forest and woodland 4,100 10 40
Unused 4,900 2 10
Ice covered 1,500 0 0
Total land 14,900 1 139
Sea 36,100 1 36
Grand total 51,000 175
• From Burns and Hardy (1975,).
300 9 Nitrogen and Sulfur Economy of SoDs

which in turn is combined with organic acids to form proteins.
NH3 + organic acids ---+ proteins
The site of N2 reduction is the enzyme nitrogenase, a two-protein complex

consisting of a larger iron- and molybdenum-containing member and a smaller
companion containing iron. Nitrogenase is indeed of great significance to hu-
mankind.
Fixation Systems. Biological nitrogen fixation occurs through a number of
organism systems with or without direct association with higher plants (Table
9.5). Included are the following.
1. Symbiotic systems, nodule-forming:

a. With legumes.
b. With nonlegumes.
2. Symbiotic systems. nonnodule forming.
3. Nonsymbiotic systems.
Although the legume symbiotic systems have received most attention his-
torically. recent findings suggest that the other systems are also very important
world-wide and may even rival the legume-associated systems as suppliers
of biological nitrogen to the soil. Each major system will be discussed briefly.
TABLE 9.5 Information on Different Systems of Biological Nitrogen Fixation"
Organisms Plants Site of

N·fixing systems involved involved fixation
Symbiotic
Obligatory
Legumes Bacteria Legumes Root nodules
(Rhizobium)
Nonlegumes Actinomycetes Nonlegumes Root nodules
(angiosperms) (Frankia) (angiosperms)
Associative
Morphological Blue-green algae. Various higher Leaf and root nodules.
involvement bacteria plants and lichens
microorganisms
Nonmorphological Blue-green algae, Various higher Rhizosphere
involvement bacteria plants and (root environment)
microorganisms Phyllosphere
(leaf environment)
Nonsymbiotic Blue-green algae. Not involved Soil. water
bacteria with plants independent of
plants
• Modified from Burns and Hardy (1975).
9.13 Biological Nitrogen Fixation 301

(a) (b)
FIGURE 9.6 Photos illustrating soybean nodules.

In (a) the nodules are seen on the roots of the
soybean plant, and a closeup (b) shows a few of
the nodules associated with the roots. A scanning
electron micrograph shows a single plant cell within
the nodule stuffed with the bacterium Rhizobium
japonicum. [(c) courtesy of W. J. Brill, University
of Wisconsin.]
(e)

9.14 Symbiotic Fixation with Legumes
Bacteria of the genus Rhizobium in association with legumes provide the major
biological source of fixed nitrogen in agricultural soils. These organisms invade
the root hairs and the cortical cells, ultimately inducing the formation of nodules
that serve as a home for the organisms (Figure 9.6). The host plant supplies
the bacteria with carbohydrates for energy, and the bacteria reciprocate by
supplying the plant with fixed nitrogen compounds. This living together or
symbiosis is mutually beneficial.
Organisms Involved. There is considerable specificity between Rhizobium

species and the host plants they will invade. A given Rhizobium species will
inoculate some legumes but not others. This specificity of interaction is the
basis for classifying rhizobia and their host plants into seven so-called cross-
inoculation groups (Table 9.6). Those legumes that can be inoculated by a
given Rhizobium species are included in the same cross-inoculation group.
Thus Rhizobium trifolii inoculates Trifolium species (most clovers), Rhizobium
phaseoli inoculates Phaseolus vulgaris (dry beans), and so on.
In areas where a given legume has been growing regularly, the appropriate
species of Rhizobium may well be present in the soil. All too often, however,
the natural Rhizobium population in the soil is too low, or the strain of the
Rhizobium species present is not effective in stimulating nodule formation
or in enhancing nitrogen fixation once the nodules have formed. It is necessary
TABLE 9.6 Cross-inoculation Groups of Legumes and Associated Rhizobia
Rblzobium
Group species Legume
Alfalfa R. meliloti Melilotus (certain ciovers). Medieago (alfalfa).

Trigonella (fenugreek)
Clover R. trifolii Trifolium spp. (ciovers)
Soybean R. japonicum Glycine max (soybeans)
Lupini R.lupini Lupinus (lupines). Ornithopus spp.
(serradella)
Bean R. phaseoli Phaseolus Vulgaris (dry bean)
Phaseolus Goccineus (runner bean)
PeBS and vetch R. leguminosarum Pisum (peas). vieia (vetch
Lathyrus (sweet pea). Lens spp. (lentil)
Cowpea miscellany Various Vigna (cowpea). Lespedeza (lespedeza).
Archis (peanut). Stylosanthes (stylo).
Desmodium (desmodium). Gajanus (pigeon
pea). Grotolaria (crotalaria). Pueraria
(kudzu)
9.14 Symbiotic Fixation with Legumes 303

TABLE 9.7 Average Yield of Soybeans as Af-
fected by the Application of different Strains of
Inoculant Containing Rhizobium japonicum
(1975-76)-
The inoculant was applied in the row on a soil
very low in organism numbers.
Inoculum Yield of
Inoculant population soybeans
strain (107 MPN/g)b (kg/ha)
No. 110 (single strain) 2.8 3565

No. 138 (single strain) 6.3 3468
Commercialc 2.3 3660
Gontrol 1139
- From Bezdicek et a1. (1978).

b MPN = most probable number.
c Specific strain not known.
in such circumstances to apply special cultures of rhizobia either by coating

the legume seeds with the culture or by applying the inoculant directly to
the soil. Effective and competitive strains of rhizobia are available commer-
cially and are widely used. In situations where the natural rhizobia strains
are low in numbers or are ineffective. significant yield increases are obtained
from using inoculants (Table 9.7). In the United States most of the inoculant
sold is used for soybeans. although some is used for forage legumes.
Quantity of Nitrogen Fixed. The rate of biological fixation of nitrogen is greatly

dependent on soil and climatic conditions. The leg~hizobia associationjl
generally function best on soils that are not too acid and tliat are well supplied
'-WfthpliosQhorus. potassium. and sulfur. Likewise. deficiencies of molybdenum.
boron. cobalt. and iron will ·limit fixation rates. In co~trast. high levels of
available nitrogen. whether from the soil or added in fertilizers·. tend to depress
biological nitrogen fixation (Figure 9.7). Apparently the system to provide com-
bined nitrogen tends to operate only when the nitrogen is needed by the plant.
From experiments around the world; it is possible to suggest typical levels
of nitrogen fixation. not only by iegume-associated organisms but by other
mechanisms as well. Such levels are shown in Table 9.8. While these levels
would not pertain to any specific ecologiCal condition. they do give an idea
as to the relative levels of fi"ation that occur. It is well to note that the legume
complexes fix large quantities of nitrogen. a fact of extreme importance today
and likely one of even greater importance in the future if energy costs fOf
commercial fertilizer continue to rise.

160~---------------------------------------------------'
Total nitrogen
tl
'",..
Q.
~ 80
o Nitrogen fixed by rhizobia
u
.:
'"
~
g
z
40
Nitrogen from
fertilizer
o 20 40 80 120 160 200

Rate of nitrogen application (mg/pot)
FIGURE 9.7 Influence of added inorganic nitrogen on the total nitrogen in clover
plants, the proportion supplied by the fertilizer and that fixed by the rhizobium organisms
associated with the clover roots. Increasing the rate of nitrogen application decreased
the amount of nitrogen fixed by the organisms in this greenhouse experiment. [From
Walker et al. (1956).]
9.15 Fate of Nitrogen Fixed by Legume Bacteria

The nitrogen fixed by the nodule organisms goes in four directions. First it is
used directlw the host plant, which thereby benefits grgatJ.y-1r.om the sym-
biosis describeJLilLSection 9.14. Second. as the nitrogen passes into the sOIl
itself, eitheLby. excretion or mor~p.rob~ by sloughing off of the roots and
especially': of the nodules._some_of it is mineralized and becomes available
a lmost immediately as ammonium or nitrate compounds. Because of the rela-
tiVely low carboD!nitrogen ratios of such residues (about 20:1) mineralization
takes place sufficiently rapid that some of the nitrogen is available to any
crop being grown in association with the legume. The vigorous development
of a grass in a legume-grass mixture is evidence of this rapid release (Figure
9.15 Fate of Nitrogen Fixed by Legume Bacteria 305

TABLE 9.8 Typical Levels of Nitrogen Fixation from Different Systems
Typical levels of
nitrogen fixation
Crop or plant Associated organism (kg/ha N per yr)
Symbiotic
Legumes (nodulated) Bacteria (Rhizobium)
Alfalfa (Medicago sativa) 150-250
Clover (Trifolium protense L.) 1~150
Soybean (Glycine max L.) 50-150
Cowpea (Vigna unquiculata) 50-100
Lupine (Lupinus) 50-100
Vetch (Vicia vilbosa) 50-125
Bean (Phaseolus vulgaris) 30- 50
Nonlegumes (nodulated)
Alders (Alnus) Actinomycetes (Fronkia) 50-150
Species of Gunnero Blue-green algae (Nostoc) 10- 20
Nonlegumes (nonnodulated)
Pangola grass (Degetaria decumbens) Bacteria (AzospirilJum) 5- 30
Bahia grass (Paspalum notatum) Bacteria (Azotobacter) 5-30
Azolla Blue-green algae (Anabaena) 150-300
Nonsymbiotic Bacteria (Azotobacter. 5- 20
Clostridium)
Blue-green algae (various) 10- 50
9.8). Third, when a legume sod is turned under or when the legume is killed
by a herbicide in a no-till cropping system, the entire root system is subject
to breakdown. Some of the nitrogen is converted to ammonia and nitrate.
and is assimilated by succeeding crops grown in the rotation.
The fourth pathway for the fixed nitrogen is to be incorporated into the
bodies of the general-purpose decay organisms and finally into the soil organic
matter. This process of immobilization was discussed in Section 9.4.
9.16 Do Legumes Always Increase Soil Nitrogen?

Because of their overall beneficial effect on crop production, one might assume
that the legume/rhizobia symbiosis would result in an increase in soil nitrogen.
It is true that the soil on which a legume has been grown will likely be higher
in nitrogen than if a nonlegume had been grown during the same period. How-
ever, even the legume may not increase the soil nitrogen since the legume
crop may utilize not only the nitrogen fixed by the rhizobia but additional
nitrogen from the soil as well. This is true especially in soils with relatively
high nitrogen contents. Crops such as beans and peas and even soybeans
and peanuts may leave the land depleted of nitrogen, since they support low
levels of fixation and in some cases their roots are removed in harvesting.
306 9 Nitrogen and Sulfur Economy of sons

Ryegrass grown with Ladino clover
3.4
3.0
~
'"~
....
I)j)
~ 2.6
'+-
...c
0
~
c
0
u
.
c
I)j)
2.2
g
Z
n alone
R yegrass groW
1.8
1.4 '--'-_ _ _ _-'-_ _ _ _ _-.1.._ _ _ _ _ _ _ _ _ _- ' -_ _ _ _- . 1 . . _

7/30 9/25 11/29 3/19 5/14
Dates of cuttings, 1979-80
FIGURE 9.8 Nitrogen content of five field cuttings of ryegrass grown alone or with
Ladino clover. For the first two harvests, nitrogen fixed by the clover was not available
to the ryegrass and the nitrogen content of the ryegrass forage was low. In subsequent
harvests. the fixed nitrogen apparently was available and was taken up by the ryegrass.
This was probably due to the mineralization of dead Ladino clover root tissue. [From
Broadbent et al. (1982).]
In general. however. the net draft of legumes on the soil nitrogen is less
than that of nonlegumes. and in some situations soil nitrogen is actually in-
creased through legume cropping. Consequently the use of legumes is encour-
aged in a rotation where the maintenance of nitrogen is important. Legumes
are usually so economical in their use of soil nitrogen that a high-protein crop
can be harvested with little or no draft on the soil nitrogen. Thus. they are
nitrogen savers. This is an important fertility axiom.
9.17 Symbiotic Fixation with Nodule-Forming

Nonlegumes
About 160 species from 13 genera of nonlegumes are known to develop nodules
and to accommodate symbiotic nitrogen fixation (Bond. 1977). Included is an
important group of angiosperms. listed in Table 9.9. The roots of these plants.
9.17 Symbiotic Fixation with Nodule-Fonning Nonlegumes 307

TABLE 9.9 Number and Distribution of Major Actinomycete-Nodulated Nonlegume
Angiosperms-
In comparison there are about 13.()()(} legume species.
Speciesb Geographic
Genus Famlly nodulated distribution
Alnus Betulaceae 33/35 Cool regions of the northern

hemisphere
Ceanothus Rhamnaceae 31/35 North America
Myrica Myrlcaceae 26/35 Many tropical. subtropical
and temperate regions
Casuarina Casuarinaceae 24/25 Tropics and subtropics
Elaeagnus Elaeagnaceae 16/45 Asia. Europe. N. America
Coriaria Corlariaceae 13/15 Mediteranean to Japan. New
Zealand. Chile to Mexico
• Selected from Torrey (1978).

b Number of species nodulated/total number of species in genus.
which are present in some forested areas and wet lands, are inoculated by
soil actinomycetes of the genus Frankia. The actinomycetes invade the root
hairs and distinctive nodules form. The rates of nitrogen fixation per hectare
compare very favorably with those of the legume/rhizobia complexes (Table
9.8). On a worldwide basis the total nitrogen so fixed may even exceed that
due to legumes (Table 9.4). While the rates of cycling of the fixed nitrogen
may not be quite as high as those associated with agricultural crops, the total
quantity fixed places the actinomycete-induced fixation on a par with rhizobia
fixation.
Certain blue-green algae are known to develop nitrogen fixing symbiotic
relations with green plants. One involves nodule formation of the stems of
Gunnera. an angiosperm common in marshy areas of the southern hemisphere.
Algae of the genus Nostoc are involved and the rate of fixation is typically
10-20 Kg/ha of nitrogen per year (Table 9.8).
9.18 Symbiotic Nitrogen Fixation Without Nodules
Recent studies have called attention to several significant nonlegume symbiotic

nitrogen fixing systems that do not involve nodules. Among the most significant
are those involving blue-green algae. One system of considerable practical
importance is the AzollalAnabaena complex, which flourishes in certain rice
paddies of tropical and semitropical areas (Lumpkin and Plucknett, 1982). The
Anabaena blue-green algae inhabit cavities in the leaves of the floating fern

Azolla and fix quantities of nitrogen comparable to these of the better rhizobia/
legume complexes (Table 9.8).
A more widespread but less intense nitrogen-fixing phenomena is that
which occurs in the rhizosphere or root environment of nonlegumes and espe-
cially grasses (Dobereiner, 1978). The organisms responsible are bacteria, espe-
cially those of the Spirillum and Azotabacter genera (Table 9.8). The organisms
use root exudates as sources of energy for their nitrogen-fixing activities. There
are differences of opinion as to the rates of fixation that occur in the rhizosphere.
Relatively high values have been observed in association with certain tropical
grasses, but rates of 5-30 kg/ha per year are thought to be more typical. Even
so, because of the vast areas of tropical grasslands, the total quantities of
nitrogen fixed by rhizosphere organisms is likely very high (Table 9.4).
9.19 Nonsymbiotic Nitrogen Fixation
There exist in soils and water certain free-living microorganisms that are able
to fix nitrogen. Since these organisms are not directly associated with higher
plants the transformation is referred to as nonsymbiotic or free-living.
Fixation by Heterotrophs. Several different groups of bacteria, and btue-green

algae, are able to fix nitrogen nonsymbiotically. In uplandm ineral :soils the
major fixation is brou8iifaDoUf1jy species of1WO genera· of heterotrophic aero-
bic bacteria: Azotobacter (in temperate zone soils) and Beijerinckia (in tropical
soils). Certain anaerobic bacteria of the genus Clostridium are also able to
. fix nitrogen. Because of pockets of low oxygen supply in most soils even when
they are in the best of tilth, aerobic and anaerobic bacteria probably work
side by side in many agricultural soils. The amount of ·nitrogen fixed by these
heterotrophs varies greatly with the pH, soil nitrogen" level, and sources of
organic matter available to them for energy. Azotobacter s ecies are sensitive
to soil pH, their activity. drop'ping off at p'H values less than 6.0. Clostridium
and Beijerenckia species are tolerant of wider pH levels. In any case, under
norm~l agricultural conditions the rates of nitrogen fixation by these organisms
are thought to be much lower th~ated with legumes, being_in
the range of 5-20 kg/ha per ~ear (Tiiole 9.8) .
.- KInong the autotrophs able to fix nitrogen are certain photosynthetic bacte-
ria and blue-green algae. (Havelka et al., 1982). In the presence of light these
organisms are able to fix their own CO~ while simultaneousiy fixing nitrogen.
The contribution of the photosynthetic bacteria is uncertain but those Of blue-
green algae are thought to be of some significance, especially in wetland areas
and in rice paddies. In some cases, these algae have been found to' fix sufficient
nitrogen for moderate rice yields, but normal levels may be no more than
9.19 Nonsymbiotic Nitrogen Fixation 309

20-30 kg/ha per year. Nitrogen fixation by blue-green algae in upland soils
also occurs but the level is much lower than is found under wetland conditions.
9.20 Addition of Nitrogen to Soil in Precipitation

The atmosphere contains ammonia and compounds released from the soil and
plants as well as from the combustion of coal and petroleum products. Nitrates
are there too in small quantities. probably resulting from electrical discharges
(lightning) in the atmosphere. These atmosphere-borne nitrogen compounds
are added to the soil through rain and snow. Although the rates of addition
per hectare are small. the total quantity of nitrogen added is not insignificant.
The amount of ammonia and nitrates in precipitation varies markedly
with location and with season. The additions are greater in the tropics than
in humid temperate regions and larger in the latter than under semiarid climates.
Rainfall additions of nitrogen are highest near cities and industrial areas and
near huge animal feedlots. In Table 9.10 will be found some of the more impor-
tant data regarding the amounts of nitrogen thus added to the soil in various
parts of the world. The figures are for the most part from temperate regions.
The ammonium nitrogen added to the soil in precipitation is generally
larger in amount than that in the nitrate form. The nitrate nitrogen is about
the same for most locations. but the ammonium form shows wide variations.
The range in total nitrogen added annually is 1-20 kg/ha. A figure of 5-8
kg/ha would be typical of that found in temperate regions. This annual acquisi-
tion of nitrogen in a readily available form to each hectare of land affords
some aid in the maintenance of soil fertility.
TABLE 9.10 Amounts of Nitrogen Brought Down in Precipitation Annuallya
Years Ammoniacal nitrogen Nitrate nitrogen

of Rainfall
Location record (In.) kg/ha lb/A kg/ha lb/A
Harpenden.
England 28 28.8 2.98 2.64 1.49 1.33
Garford. England 3 26.9 7.20 6.43 2.16 1.93
Flahult. Sweden 1 32.5 3.72 3.32 1.46 1.30
Griiningen.
Holland 27.6 5.08 4.54 1.64 1.46
Bloemfontein
and Durban.
South Africa 2 4.50 4.02 1.58 1.39
Ottawa. Canada 10 23.4 4.95 4.42 2.42 2.16
Ithaca. N.Y. 11 29.5 4.09 3.65 0.77 0.69
• From Lyon et al. [1952}.

9.21 Reactions of Nitrogen Fertilizers
Nitrogen applied in fertilizers undergoes the same kinds of reactions as does
nitrogen released by biochemical processes from plant residues. Most of the
fertilizer nitrogen will be present in one or more of three forms: (a)~,
(b) amm nia, and (c) urea. The fate of each of these forms has already been
discussed briefly. Thus, urea nitrogen is subject to ammonification, nitrification,
and utilization by microbes and higher plants. Ammonium fertilizers can be
oxidized to nitrates, fixed by the soil solids, or they can be utilized without
change by higher plants or microorganisms. And nitrate salts can be lost by
volatilization or leaching or they can be absorbed by plants or microorganisms.
High Concentrations. One important fact should be remembered when dealing

with the reaction of fertilizer nitrogen. The added fertilizer salts will almost
invariably be localized and in higher concentrations than found in the bulk
of the soil. For this reason, the usual reactions are sometimes subject to modifi-
cation.
When anhydrous ammonia, ammonium-containing salts, or even urea is
added to highly alkaline soils, some nitrogen loss in the form of free ammonia
is likely. Also, under these conditions, the nitrification process is inhibited,
only the first step proceeding normally. Nitrates may thus accumulate until
much of the ammonium form has been oxidized. Only then will the second
step, that of nitrate formation, take place at normal rate.
The addition of large amounts of nitrate-containing fertilizers may affect
the processes of free fixation and gaseous nitrogen loss. In general, fixation
by free-living organisms is depressed by high levels of mineral nitrogen. Gase-
ous losses, on the other hand, are often encouraged by abundant nitrates.
Heavy nitrate fertilization would thus tend to increase losses of nitrogen from
the soil.
In most soil situations the effects of higher localized concentrations of
fertilizer materials on nitrogen transformations are not serious. Consequently,
it can be assumed that fertilizer nitrogen will be changed in soils in a manner
very similar to that of nitrogen released by biological transformations.
Soil Acidity. Ammonium-containing fertilizers and those that form ammonia

upon reacting in the soil have a tendency to increase soil acidity (see Section
18.11 for a more thorough discussion of this). The process of nitrification (see
the equations in Section 9.7) releases hydrogen ions that become adsorbed
on the soil colloids. For best c 'n humi ions, continued and
substantial u~e of acid-forming fertiliz~rs.mu~BJ;kom anied b ap lications
of lime.
TIle nitrate component of fertilizers does not increase soil acidity. In fact,
nitrate fertilizers containing cations in the molecule (for example, sodium ni-
trate) have a slight alkalizing effect.
9.21 Reactions of Nitrogen Fertilizers 311

9.22 Practical Management of Soil Nitrogen
The problem of nitrogen control is twofold: (a) the mainte nance of an
adequ ate
nitrogen supply in the soil and (b) the regulation of the nitrogen turnov
er to
assure a ready availability to meet crop demands.
Nitrogen Balance Sheet. Major gains and losses of availab le soil

nitrogen
are diagrammed in Figure 9.9. While the relative additions and losses by
variou s
mechanisms will vary greatly from soil to soil. the principles illustra
ted in
the diagram are valid.
The major loss of nitrogen from most soils'is that removed in crop plants.
A good crop of wheat or cotton may remove only 100 kg/ha of nitroge
n. nearly
half of which may be returne d to the soil in the stalks or straw. A
bumpe r
silage corn crop. in contrast. may contain over 250 kg/ha and a good
yield
of alfalfa or of well-fertilized grass hay more than 300 kg/ha. It is
obvious
that modern yield levels require nutrient inputs far in excess of those
of a
generation ago.
Erosion. leaching. and volatilization losses are determ ined to a large degree
by water management practices. Their magnitudes are so depend ent
upon spe-
cific situations that generalizations are difficult. However. soil and crop
man-
agement practices which give optimum crop yields will likely hold these
source s
of nitrogen loss to a satisfactory minimum.
Meeting the Deficit. In practice. nitrogen deficits are met from four
sourc es-
crop residues. farm manure. legumes. and commercial fertilizers. On dairy
farms
and beef ranches. much of the deficit will be met by the first three
methods.
fertilizers being used as a supplementary source. On most other types
of farms.
however. fertilizers will play a major role. Where vegetables and other
cash
FIGURE 9.9 Major gains and losses Nitrogen fixation Commer cial fertilizer
_____ _ _____ _
of availab le soil nitrogen. The widths ~
~A~
~
of the arrows indica te roughly the Symbiot ic

magnitude of the losses and the
additio n often encountered. It should
be emphas ized that the diagram
l
represe nts average conditions only
and that much variability is to be Rain
expecte d in the actual and relative Available
quantit ies of nitrogen involved. Soil organic - -...~ soil nitrogen 1--- --" Atmosphere
matter ----L ,.-__ --.r-_ _......-
J Volat ilization
Crop removal Leaching losses Erosion losses

crops with high nutrient requirements are grown, the nitrogen deficit will be
met almost entirely with commercial fertilizers. Even with the general field
crops, modern yield levels can be maintained only through the extensive use
of fertilizers.
Turnover Regulations. By all odds, the more difficult of the two general prob-
lems of nitrogen control is the regulation of this element after it enters the
soil. Availability at the proper time and in suitable amounts, with a minimum
of loss, is the ideal. Even where commercial fertilizers are used to supply
much of the nitrogen, maintaining an adequate but not excessive quantity of
available nitrogen is not an easy task.
Soils under any given climate tend to assume what may be called a normal
or equilibrium content of nitrogen. Thus, under ordinary methods of cropping
and manuring, any attempt to raise the nitrogen content to a point materially
higher than this normal will be attended by unnecessary waste due to drainage
and other losses. At the same time, the nitrogen should be kept suitably active
by the use of legumes and other organic materials with a low C/N ratio and
by the applications of lime and commercial fertilizers.
This is essentially the recommendation already made for soil organic mat-
ter (Section 8.18), and it is known to be both economical and effective. In
short, the practical problem is to supply adequate nitrogen to the soil, to keep
it mobile, and to protect it from excessive losses caused by leaching, volatiliza-
tion, and erosion.
9.23 Importance of Sulfur
Sulfur has long been recognized as essential for plant and animal growth.
Although much is yet to be learned about the functions of this element, it is
already known to be indispensable for many reactions in every livin cell.
Sulfur is a constituent 0 the amino aCI s methionine, cysteme, an cystine,
deficiencies of which result in serious human malnutrition. The vitamins biotin,
thiamine, and Bl contain sulfur, and the structure of proteins is determined
to a considerable extent by sulfur groups. The properties of certain protein
enzymes, such as those concerned with photosynthesis and nitrogen fixation,
are thought to be attributable to the type of sulfur linkages present. As with
the other essential elements, sulfur plays a unique role in plant and animal
metabolism.
Plants that are sulfur deficient are characteristicall small and spindly.
The youn ill' eaves are light reen to e OWlS , and in the case 0 e umes
110 u ation of the roots is reduG.-ed. Protein quality, especially methionine con-
tent, suffers in sulfur-deficient plants. The maturity of fruits and seeds is delayed
in the absence of adequate sulfur.
9.23 Importance of Sulfur 313

Deficiencies of Sulfur. It is only in recent years that deficiencies of sulfur
have become common. Since it was first manufactured in 1840, sulfur-bearing
Si.i.jieijiliosphate has helped meet the needs for this element. Likewise, ammo-
nium sulfate, long a significant constituent of fertilizers, has been an important
sulfur source. Atmospheric sulfur dioxide, a by-product of the combustion of
sulfur-rich coals and residual fuel oilS,has supplied large quantities of t1i1s
element to botli plants and soils. Thus, oy seemingly incioental means tfie-
su lfur neeas of crops in the past have been largely satisfied, especially in
areas near industrial centers (Table 9.11).
In recent years, increased demand for high-analysis fertilizers has forced
manufacturers to use alternatives to superphosphate and ammonium sulfate.
Ammonium sulfate supplied 31% of the world's nitrogen in 1960, but only 8%
in 1980; superphosphate as the world's source of phosphorus declined from
55% in 1960 to 20% in 1980 (IFDC, 1979). As a result, many sulfur-free fertilizers
are on the market, and the average sulfur content of fertilizers has decreased.
Even sulfur-containing pesticides, so commonly used a few years ago, have
been largely replaced by organic materials free of sulfur.
The replacement of wood and coal for domestic heating by natural gas,
electricity, and low-sulfur fuel oil has affected the amount and distribution
of sulfur dioxide in the atmosphere. Intensified efforts in the United States
to reduce air pollution in and around cities and industrial areas will likely
further reduce the quantity of sulfur in the atmosphere. The recognition that
clean air is a primary goal will necessitate finding alternative means of supply-
ing sulfur for plant growth.
Coupled with these reductions in the supply of sulfur to soils and plants
is the greater removal of this element in harvested crops. Yields have increased
markedly during the past 20-25 years, and much of the sulfur removed in
crops has not been returned. The quantity of sulfur thus removed is about
the same as that of phosphorus. It is not surprising, therefore, that increased
attention is being given to sulfur.
TABLE 9.11 Sulfur Collected in Precipitation at Rural. Urban and Industrial

Locations in Southern and Midwestern United States"
Sulfur collected (kg/ha per year)

No. of
State Year locations Rural Urban Industrial
Iowa 1971-73 6 16.0 16.8

South Carolina 1973-75 15 6.2 11.3 11.2
Wisconsin 1969-71 20 16.0 42.0 168.0
Tennessee 1973-76 5 18.1
• Data from several sources cited by Jones and Suarez (1980).

Areas of Deficiency. Sulfur deficiencies are widespread throughout the world,
but are more prevalent in areas where soil parent materials are low in sulfur,
where extreme weathering and leaching has removed this element, or where
there is little replenishment of sulfur from the atmosphere. In many tropical
countries one or more of these conditions prevail and sulfur-deficient areas
are common (IFDC, 1979). In the United States, deficiencies of sulfur are most
common in the southeast, the northwest, California, and the Great Plains. In
the northeast and in other areas with heavy industry and large cities, sulfur
deficiencies do not seem to be widespread (Figure 9.10).
Crops vary in their sulfur requirements. Legume crops such as alfalfa,
the clovers, and soybeans have high sulfur requirements as do cotton, sorghum,
sugar beets, cabbage, turnips, and onions. Forests and grasses and cereals
generally have lower sulfur requirements, although wheat in the northwestern
states is often quite responsive to sulfur applications.
9.24 Natural Sources of Sulfur

There are three major natural sources from which plants can be supplied with
available sulfur: (a) soil minerals, (b) sulfur gases in the atmospher!h and (c)
organically bound sulfur. These will be considered in order.
SolI Minerals. There are several soil minerals in which sulfur is combined
and from which it may be released for growing plants. For example, sulfides
of iron, nickel, and copper are found in many soils, especially those with re-
stricted drainage. They are quite abundant in soils of tidal marsh areas. Upon
oxidation, the sulfides are changed to sulfates, which are quickly available
for plant use.
In regions of low rainfall, sulfate minerals are common in soils. Accumula-
tions of gypsum in the lower horizons of Mollisols and Aridisols (see Figure
13.10) are examples. Accumulations of soluble salts, including sulfates in the
surface layers, are characteristic of saline soils (see Figure 6.14) of arid and
semiarid regions. When the soils are dry, the salt accumulations are visible.
The accumulation of sulfates in subsoils is not limited to areas of low
rainfall. For example, in the southeast, higher sulfate contents are often found
in the subsoils than in the topsoils. Apparently, the sulfates are absorbed by
the acid iron and aluminum oxide and kaolinitic clays that are usually present
in larger quantities in the subsoil.
Abnospheric Sulfur.3 The combustion of fuels, especially coal, releases sulfur

dioxide and other sulfur compounds into the atmosphere. In fact, the content
of sulfur in the air is generally directly related to the distance from industrial
3 For a discussion of this topic see Terman (1978).
9.24 Natural Sources of Sulfur 315

United States
Alabama Missouri
Alaska Montana
Arkansas Neb raska
California North Carolina
Colorado North Dakota
Florida Ohio
South and
Georgia Oklahoma
Central America
Hawaii Oregon
Idaho Pennsylvania Argentina
Ill inois South Carolina Brazil
Indiana South Dakota Chile
Iowa Tennessee Colombia
Kansas Te xas Costa Rica
Louisiana Virginia EI Salvador
Maryland Washington Honduras
Michigan Wisconsin Puerto Rico
Minnesca Wyoming Venezuela
Mississippi Windward Islands
Europe
or..'~'
Belgium
Bulgaria
Ireland
Italy
1/':
Czechoslovak ia Netherlands
Denmark Norway
England Poland
Finland Spain
France Sweden
Germany U.S.s.R .
Iceland Yugoslavia
Africa
Cameroon Mozambique
Central African Nigeria
Republic Senegal
Chad South Africa
Congo Tanzania Australasia
Ghana Togo Burma
Guinea Uganda i Australia
India
Ivory Coast Upper Volta Indonesia ... Fij i
Kenya Zaire New Guinea
Lebanon New Zealand
Mali Zambia Malaysia
Malawi Zimbabwe ~olomon Islands
Sri Lanka
Taiwan 17
Thailand (f
FIGURE 9.10 Locations throughout the world where sulfur deficiencies have been
reported. Other sulfur-deficient areas undoubtedly exist. but have yet not been identified.
[Courtesy The Sulphur Institute.]
centers (Figure 9.11). Except near seashores, where salt spray adds sulfur in
significant quantities, and near marshes, which are sources of hydrogen sulfide,
the combustion of coal is the most significant source of atmospheric sulfur.
Atmospheric sulfur becomes part of the soil-plant system in three ways.
Some of it is absorbed directly from the atmosphere by growing plants. A
considerable quantity is absorbed directly by the soil from the atmosphere,
and a similar amount is added with precipitation.
The quantity of sulfur absorbed directly by plants from the atmosphere
will vary with atmospheric and soil conditions. Experiments have shown that
even plants supplied with adequate soil sulfate can absorb 25-35% of their
sulfur from the atmosphere. If the soil sulfur is low and the atmospheric sulfur
high, about half of the plant sulfur can come from the atmosphere.
Data presented graphically in Figure 9.11 show a comparison of direct
soil absorption of sulfur and the addition of this element in precipitation. At
least in this instance, the quantity directly absorbed from the soil was some-
what greater than that from the precipitation.
Average sulfur content of air (pg/m 3 air)

.
78~~
4~5 ____~4r
3 ____________~ 3 ____________________________~
2r 11
7
Sulfur added directly from air during 6 yr period
6
"~I Sulfur added with precipitation during 6 yr period
'0
..e:
~
.
::I
~
4
::I
V1
3
"
~~~~~~;'-~~'~",,~:,:::.~~:,,~,:::~'0~~~':::::::::::,- ~'-::':::-.::-.."""'~",-:: 0:'~,,:-,
1
o ~~ ______ ~ ____________ ~ ________________________ ~
1 2 4 6 8
Distance from plant (km)
FIGURE 9.11 Sulfur added to soils as affected by distance from an oil-burning

industrial plant in Sweden. Note the rapid dropoff in sulfur added directly from the
air. [From O. Johannson (1960).]
9.24 Natural Sources of Sulfur 317

The quantity of sulfur added in precipitation or absorbed directly varies
according to the content of this element in the atmosphere. Samplings for sulfur
in precipitation show variations in annual accretions from less than 1 to nearly
100 kg/ha (Coleman. 1966). Data in Table 9.11 indicate levels found in several
locations in the United States.
It is not surprising that soils absorb atmospheric sulfur directly or that
this element moves in through rain and snow. The sulfur dioxide forms sulfurous
acid (H 2S0 3 ) when in contact with water or with water vapor. Any sulfur
trioxide present would form sulfuric acid by the same process. These strong
acids are readily absorbed by soils.
Recent environmental concerns about high sulfur levels in the atmosphere
are of great practical significance to agriculture. On the one hand efforts to
reduce atmospheric sulfur are welcomed in areas near industrial plants. where
toxic effects of high sulfur levels on vegetation are noted. But in much wider
areas drastic reductions in atmospheric sulfur would result in deficiencies of
this element for optimum crop growth. In these cases the sulfur deficiency
would need to be met by increasing the sulfur content of fertilizers. thereby
increasing crop production costs. These matters are discussed further in Chap-
ter 21.
Organic Bound Sulfur. In most humid region surface soils. about half the
sulfur is in the organic form. although the proportion would be much lower
in the subsoil. Just as is the case with nitrogen. however. all too little is known
of the specific organic sulfur compounds present. The sulfur added in plant
residues is mostly in the form of proteins. which are normally subject to rather
ready microbial attack. In some manner. the sulfur (along with the nitrogen)
is stabilized during humus formation. In this stable form or forms. it is protected
from rapid release and thus cannot be lost or taken up by higher plants. The
similarity between the general behavior of organic nitrogen and sulfur fractions
is unique.
Although the specific sulfur compounds associated with soil organic matter
are not known. the presence of some forms is strongly suspected. For example.
sulfur-containing amino acids-cystine. cysteine. and methionine-and other
compounds with direct C-S linkages are thought to be present. as are organic
sulfates.
Forms of Sulfur. This discussion has identified three major forms of sulfur
in soils and fertilizers: sulfides, sul~ and organic forms; To these must
be added the fourth important form. elemental SUlfur, the starting point of
most of the manmade chemical sulfur compounds. The following sections will
show relationships among these forms.

9.25 The Sulfur Cycle
The major transformations that sulfur undergoes in soils are shown in Figure
9.12. The inner circle shows the relationships among the four major forms of
this element in soils and in fertilizers. The outer portions show the most impor-
tant sources of sulfur and how this element is lost from the system.
Some similarity between the sulfur and nitrogen cycles is evident (compare
Figure 9.1). In each case, the atmosphere is an important source o,f the element
in question. Each is held largely in the organic fraction of the soil and each
is dependent to a considerable extent upon microbial action for its various
transformations.
Figure 9.12 should be referred to frequently as a more detailed examination
Soil Sulfides
minerals ;""'--7" (S2-)
Sulfur
(5)
FIGURE 9.12 The sulfur cycle, showing some of the transformations that occur as
this element changes form in soils, plants, and animals. It is well to keep in mind
that, except for certain soils in arid areas, the great bulk of the sulfur is in the form
of organic compounds.
9.25 The Sulfur Cycle 319

is made of sulfur in plants and soils, beginning with the behavior of this element
in soils.
9.26 Behavior of Sulfur Compounds in Soils

Mineralization. It is not surprising that sulfur behaves much like nitrogen
as it is absorbed by plants and microorganisms and moves through the sulfur
cycle. The organic forms of sulfur must be mineralized by soil organisms if
the sulfur is to be used by plants. The rate at which this occurs is dependent
upon the same environmental factors as affect nitrogen mineralization, includ-
ing moisture, aeration, temperature, and pH. When conditions are proper for
general microbial activity, sulfur mineralization occurs. The mineralization re-
action might be expressed as follows.
Organic sulfur --+ Decay products --+ Sulfates

Proteins and HIS and other
other ol'llanic sulfides are
combinations simple examples
Immobilization. Immobilization of inorganic forms of sulfur occurs when low-

sulfur, energy-rich organic materials are added to soils not plentifully supplied
with inorganic sulfur. The mechanism is thought to be the same as for nitrogen.
The energy-rich material stimulates microbial growth and the inorganic sulfur
is synthesized into microbial tissue. Only when the microbial activity subsides
does the inorganic sulfate form again appear in the soil solution.
These facts suggest that, like nitrogen, sulfur in soil organic matter may
be associated with organic carbon in a reasonably constant ratio. The ratio
among carbon, nitrogen, and sulfur for a number of soils on three different
continents is given in Table 9.12. A ratio of 130: 10: 1.3 is reasonably representa-
TABLE 9.12 Mean Carbon/Nitrogen/Sulfur Ratios in a Variety

of Soils Throughout the World-
Description
Location and number of sons C/N/S ratio
North Scotland Agricultural. noncalcareous (40) 147:10:1.4

Minnesota Mollisols (6) 114:10:1.55
Minnesota Spodosols (24) 132:10:1.22
Oregon Agricultural. varied (16) 145:10:1.01
Eastern Australia Acid soils (128) 152:10:1.21
Eastern Australia Alkaline soils (27) 140:10:1.52
• From Whitehead (1964).

tive. Undoubtedly. there is a definite relationship among the contents of these
elements. a relationship that is in accord with their behavior in soils.
9.27 Sulfur Oxidation and Reduction

During the microbial decomposition of organic sulfur compounds. sulfides are
formed along with other incompletely oxidized substances such as elemental
sulfur. thiosulfates. and polythionates. These reduced substances are subject
to oxidation. just as are the ammonium compounds formed when nitrogenous
materials are decomposed. The oxidation reactions may be illustrated with
hydrogen sulfide and elemental sulfur.
H2S + 2 O2 -+ H 2SO, -+ 2 H+ + SO,2-

2 S + 3 O2 + 2 H20 -+ 2 H 2SO, -+ 4 H+ + 2 SO,2-
The oxidation of some sulfur compounds. such as sulfites (S03 2-) and
sulfides (S2-). can occur by strict chemical reactions. However. most of the
sulfur oxidation occurring in soils is thought to be biochemical in nature. It
is accomplished by a number of autotrophic bacteria including those of the
genus Thiobacillus. five species of which have been characterized. Since the
environmental requirement and tolerances of these five species vary consider-
ably. the process of sulfur oxidation occurs over a wide range of soil conditions.
For example. it occurs at pH values ranging from less than 2 to h' her than
9. This is in contrast to ilie compara6le nitrogen 0 'llation process. nitrification:
where a rather narrow pH range near neutral is required.
Like nitrates. sulfates tend to be unstable in anaerobic environments. They
are reduced to sulfides by a number of bacteria of two genera. Desulfovibro
(five species) and Desulfotomaculum (three species). The organisms use the
combined oxygen in sulfate to oxidize organic materials. A representative reac-
tion is
2 R-CH 20H + SO,2- -+ 2 R-COOH + 2 H20 + S2-
Organic alcohol Sulfate Organic acid Sulfide
In poorly drained soils. the sulfide ion would likely react immediately
with iron. which in anaerobic conditions would be present in the ferrous form.
This reaction might be expressed as follows.
Fe 2+ + S2- -+ FeS
Iron
sulfide
Sulfur reduction takes place with compounds other than sulfates. For example.
sulfites (S032-). thiosulfates (S2032-). and elemental sulfur (S) are rather easily
reduced to the sulfide form by bacteria and other organisms.
9.27 Sulfur Oxidation and Reduction 321

The oxidation and reduction of inorganic sulfur compounds are of great
importance to growing plants. In the first place. these reactions determine to
a considerable extent the quantity of sulfate present in soils at anyone time.
Since this is the form taken up by plants. the nutrient significance of sulfur
oxidation and reduction is obvious. Second. the state of sulfur oxidation deter-
mines to a marked degree the acidity of a soil. a fact that will be considered
further below.
Sulfur Oxidation and Acidity. Sulfur oxidation is an acidifying process. The

preceding reactions of hydrogen sulfide and elemental sulfur illustrate this
point. For every- sulfqr atom oxidized. two hydrogen ions result. This effect
is utilized by adding sulfur to reduce the extreme alkalinity of certain alkali
soils of ariareglOns and to re uce the pH of certain soilSl'or the control of
diseases such as potato scab see Figure 7.11}. It is also taken into consideration
when making tlie choice of fertilizer. since some materials such as sulfur-coated
urea are acid forming.
The acidifying effect of sulfur oxidation can bring about extremely acid
soil conditions. For example. this has been known to occur when land is drained
after it has been submerged for some time under brackish water or seawater.
During the submerged period. sulfates in the water are reduced to sulfides.
in which form they are stabilized generally as iron sulfides (Bloomfield and
Coulter. 1973). Since there is a continuous supply of sulfates under these condi-
tions. high levels of sulfides are built up. If there are periods of partial drying.
elemental sulfur can form by partial oxidation of the sulfides. The sulfide and
elemental sulfur content are hundreds of times higher than would be found
in comparable upland soils.
When these areas are drained. the sulfides and! or elemental sulfur are
quickly oxidized. forming sulfuric acid. The soil pH may drop to as low as
1.5. a level unknown in normal upland soils. Obviously plant growth cannot
occur under these conditions. Furthermore. the quantity of limestone needed
to neutralize the acidity is so high as to make this remedy completely uneconom-
ical.
Sizeable areas of these kinds of soils, called acid sulfate soils or cat-clays,
are fQllnd.in.sautheast Asia and along the Atlantic~s of sOuth America ana I
Africa. They also occur in tideland areas along the coasts of several other areas,
~ing the southeastern part and the West Coast of the United States. So long
as these soils are kept submerged, the soil reaction does not drop prohibitively.
Consequently, production of paddy rice is sometimes possible under these
conditions.
Another potentially harmful effect of acid production by sulfur is the devel-
opment of acidity in fog or rain containing oxides of sulfur (Likens et al..
[1979]). The sulfuric acid resulting from reactions of these oxides with water
can lower the pH of the precipitation to 4 or below. creating problems for
plants as well as people (Section 20.13). Fortunately. steps are being taken
to reduce excess sulfur in the atmosphere.

9.28 Sulfate Retention and Exchange
Sulfate is the form in which plants absorb most of their sulfur from soils.
Since this ion is quite soluble. it would be readily leached from the soil espe-
cially in humid regions. were it not for its adsorption by the soil colloids. As
was pointed out in Chapter 4. most soils have some anion exchange capacity.
which is associated with iron and aluminum oxide clays and to a limited
extent with 1: 1-type silicate clays. The sulfate is attracted by the positive
charges that characterize acid soils containing these clays. It also reacts directly
with hydroxyl groups associated with these clays. A general equation indicates
how this may occur.
OH OH
-Ai
/"- AI- + KHSO, ~ -AI
/"- Ai- + H 0 2
"-O~ "-s6.
I
K
This reaction takes place in acid soils. If the soil pH were increased and
hydroxyl ions were added. the reaction would be driven to the left and sulfate
would be released. Thus this is an ion exchange reaction. the hydroxyl being
exchanged for an KSO. - anion.
Most soils will retain some sulfate. although the quantity held is generally
small and its strength of retention is low compared to that of phosphate. Sulfate
retention is generally higher in the subsoil than the topsoil. since iron and
aluminum oxides are more prominent in subsoils. Soils of the southeast part
of the United States tend to be higher in sulfate' adsorption than elsewhere
in the country because of their higher content of iron and aluminum oxides
and 1: 1-type silicate clays. especially in the subsoils.
Sulfur adsorption and exchange by soils is important since they can provide
a ready supply of available sulfur for plants. Sulfur retention is also of some
significance. since it helps the soil hold an otherwise mobile element that
could easily be lost by leaching.
9.29 Sulfur and Soil Fertility Maintenance

In Figure 9.13 are depicted the major gains and losses of sulfur from soils.
The problem of maintaining adequa te quantities of sulfur for minerals is becom-
ing increasingly important. Although this element is added to soils through
adsorption from the atmosphere and as an incidental component of many ferti-
lizers. each of these sources are apt to decline in the future. Even though
chances for widespread sulfur deficiencies are generally less than for the three
"fertilizer" elements. higher crop removal of sulfur makes it essential that farm-
ers be on guard to prevent deficiencies of this element.
9.29 Sulfur and Soil Fertility Maintenance 323

FIGURE 9.13 Major gains and Commercial
Crop residues
losses of available soil sulfur. This fertilizer
Manures
represents average conditions from
/
Sulfur-bearing
which considerable variation occurs minerals
in the field.
Soil organic _ _~ Rain

matter
Available
soil sulfur
\-001II---- Atmosphere
Crop removal Leaching Erosion losses
Situations where crops respond to sulfur applications are becoming more

and more common. Less "incidental" fertilizer sulfur is being added in some
areas, and additionso f this element from the atmosphere will likely continue
to decrease as air- ollution:a15atemente ffOrts are acceleratea. Furthermore,
Itleadily increasing crop yields are removID8j~!~portionatel}' arger quantities
of this and other elements. Allliough crop reslQues and farmyard manures
----.
can help rep'lenish the sulfur removed, greater and 8!'eateraependence must
be placed on fertilizer additionS:-Regular s fur applica 'ons are necessary
now for good crop yields in large areas far removed from industrial plants.
---
There will certainly be an increased necessity for and use of sulfur in the
future.
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Lumpkin, T. A., and O. L. Plucknett. 1982. Azolla as a Green Manure: Use
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Nelson, D. W., and D. M. Huber. 1980. "Performance of nitrification inhibitors
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Agron., Soil Sci. Soc. Amer.).
Nommik, N., and K. Vahtras. 1982. "Retention and fixation of ammonium and
ammonia in soils," ch. 4 in F. J. Stevenson (Ed.), Nitrogen in Agricultural
Soils, Agronomy Series No. 22 (Madison, WI: Amer. Soc. of Agron., Crop
Sci. Soc. Amer., Soil Sci. Soc. Amer.).
Patrick, W. H. Jr., and K. R. Reddy. 1977. "Fertilizer nitrogen reactions in flooded
soils," in SEFMIA, Proceedings of the International Seminar on Soil Envi-
ronment and Fertility Management in Intensive Agriculture (Tokyo: The
Society of the Science of Soil and Manure), pp. 275-281.
References 325
Stevenson. F. J. (Ed.). 1982. Nitrogen in Agricultural Soils. Agrono
my Series
No. 22 (Madison. WI: Amer. Soc-. Agron .• Crop Sci. Soc. Amer.• Soil
Sci.
Soc. Amer).
Terman. G. L.1978. "Atmospheric sulphu r-the agronomic aspects."
Tech. Bull.
23 (Washington. DC: The Sulphur Institute).
Torrey. J. G. 1978. "Nitrogen fixation by actinomycete-induced angios
perms."
BioScience. 28:586-592.
Walker. T. W .• et al. 1956. "Fate of labeled nitrate and ammonium
nitrogen
when applied to grass and clover grown separa tely and together."
Soil
Sci.. 81:339-52.
Whitehead. D. C. 1964. "Soil and plant-nutrition aspect s of the sulfur
cycle."
Soils and Fertilizers. 27:1-8.

Supply and Availability
of Phosphorus
and Pot ·sium
[Preceding page] Ample supplies of phosphorus and potassium are essential for good
crop yields. The response to additions of fertilizers containing these elements (expressed
as P205 and K20) is obvious in this photograph. [Courtesy Walt Wallingford and Crops
and Soils Magazine]
Next to nitrogen. the most critical elements in influencing plant growth and
production throughout the world are os horus and otassium Unlike nitro-
gen. however. these elements are not supp led throug Dioc emical fixation.
but must come from other sources to meet plant requirements. Included among
these sources are (a O.ID.In.lru:iaU ertilizer; (b animal Illanures' (c) pJanL esi-
• incwding greEtn manur~; (d human. in us trial! and domestic wast~ ;
and (e native compounds of these elements. both organic and inorganic. al-
ready present in the soil. Since the first four sources are to be considered in
later chapters. attention now will be focused on the ways and means of utilizing
the body of soil as a source of these mineral elements.
10.1 Importance of Phosphorus l

With the possible exception of nitrogen. no other element is as critical in
practical agriculture as is ho ho . It is a component of the two compounds
involved in the most signi cant energy transformations in plants. adenoltine
. hate ADP and adenosine triphollJ:)hate (ATP . ATP. synthesIze from
ADP throug oth respira lOn ana pliotosynthesis. contains a high-energy phos-
phate group that drives most biochemical processes requiring energy. For exam-
ple. the uptake of some nutrients (see Figure 1.15) and their transport within
the plant. as well as the synthesis of different molecules. are energy-using
processes that ATP helps to implement.
Phos horus is an essential component of deoxyribonucleic acid (DNA).
the seat of genetic inheritance in plants as well as anima s. and of the various
forms of ribonucleic acid (RNA needed for r . synthe is. Obviously. phos-
phorus is essential for numerous metabolic synthesis processes.
It is difficult to state in detail all the beneficial effects of phosphorus on
plants. Among the more significant ones are
1. Cell division and fat and albumin formation.

2. Flowering and fruiting. including seed formation.
3. Crop maturation. in which phosphorus counteracts the effects of excess
nitrogen applications.
4. Root development. particularly of the lateral and fibrous rootlets.
5. Strength of straw in cereal crops. thus helping to prevent lodging.
6. Improvement of crop quality. especially of forages and of vegetables.
1 For a review of the significance of this element see ISMA (1977).
328 10 Supply and Availability of Phosphorus and Potassium

10.2 The Phosphorus Cycle
The biological cycling of phosphorus from the soil to higher plants and return
is illustrated in Figure 10.1. Note that the plant roots absorb inorganic and
to a lesser extent organic phosphorus compounds and trans locate them to
above ground plant parts. The phosphorus in the plants is returned to the
soil either in crop residues or in human and animal wastes. Microorganisms
Crop residues
Animal manures
- ~~~~~
MICROBIAL TISSUE
AVAILABLE P r-------~ ORGANIC POOL

Inorganic
and organic
FIGURE 10.1 The phosphorus cycle in and above the soil surface. Crop residues.
human wastes. animal manures. and chemical fertilizers are the primary sources of
phosphorus. Two major pools of phosphorus are present in the soil: (a) an organic
pool found in humus and plant and microbial.residues and (b) an inorganic pool of
insoluble Ca. Fe. and A compounds. In a representative mineral soil 40-00% of the
phosphorus would be found in each of the organic and inorganic pools with about 1-
2% in the microbial form and perhaps 0.01% in the available form.
10.2 The Phosphorus Cycle 329

decompose the residues and temporarily tie up at least part of the phosphorus
in their body tissue. Ultimately it is released to become part of either the
inorganic or the organic pool of this element in the soil. In either form the
phosphorus is very slowly converted to the available forms that plant roots
can absorb, thereby starting a repeat of the cycle.
In most soils, the amount of phosphorus in the available form at anyone
time is very low, seldom exceeding about 0.01% of the total phosphorus in
the soil. It is for this reason that available phosphorus levels must be
supplemented on most soils by adding chemical fertilizers. Unfortunately, much
of the phosphorus thus supplied is converted to the less available inorganic
pool, in which form it is released very slowly and is usable by plants only
over a period of years. The problem of maintaining phosphorus in an available
form will receive our attention next.
10.3 The Phosphorus Problem

While the phosphorus content of an average mineral soil compares favorably
with that of nitrogen, it is much lower than potassium, calcium, or magnesium
(see Table 1.3). Of even greater importance, however, is the fact that most
os horus present in soils is not readily available to p'lants. so,
when soluble fertilizer salts of this element are suppliea to soils their phospho-
rus is often fixed 2 or rendered insoluble or unavailable to higher plants, even
under the most ideal field conditions (see Section 10.7).
Fertilizer practices in many areas exemplify the problem of phosphorus
availability. Large quantities of phosphate fertilizers are applied to soils. The
removal of phosphorus from soils by crops, however, is low compared to that
of nitrogen and potassium, often being only one third or one fourth that of
the latter elements. The necessity for high fertilizer dosage when relatively
small quantities of phosphorus are being removed from soils indicates that
much of the added phosphates becomes unavailable to growing plants. It also
suggests some soil phosphorus accumulation.
In the United States, phosphorus added in fertilizers in the past 20 years
has generally exceeded that removed by crops (Figure 10.2). In some areas,
notably the eastern seaboard states, additions of phosphorus have greatly ex-
ceeded the removal of this element by crops. Since phosphorus is only sparingly
removed by leaching, this utilization of phosphate fertilizers is obviously ineffi-
cient. Research has quantified this inefficiency by showing that less than 15%
of ferh lze - ie1i phosM orus is normally taken up by the cro during the
ear tne fertilizer was a liea.
riefly, then, the overall phosphorus problem is threefold: (a a com ara-
2 Note that the term fixed has a different meaning for phosphorus and potassium than for
nitrogen. Nitrogen fixation refers to the conversion of N2 gas to combined forms that plants can
utilize. Phosphorus and potassium fixation refers the IlD.Il.ersion of solubl Qr!lllI of these
elements to insoluble forms unavaila e 0 pants.

2.5
Estimated P
2.0 apPJlied to crops ,. _ ,
-_ /
-;;;-
c: .,.-- ,.. _, 7 £_ _. 1
~
o
';; ' .5
.,. .,.----~
'E P removed by crops
'"2
,g ' .0
~
o
..c:
CI..
0. 5
1965 1970 1975 1980 1982

FIGURE 10.2 Estimates of fertilizer phosphorus applied in the United States from
1965 to 1982 compared to the removal of this element by crops. [From Douglas (1982).]
tiy'eJy low Ie el of total Rhosphorus in soils, (b) ,l.a.w"ay-ailability of this native

Rhosphorus, and (c) !'ked aUo of added soluble phosp'hates. Since
crop removal of phosphorus is relatively low and Id hospb.ate supplies
are huge, the problem of supplying sufficient total phosphorus is a matter of
economics and distribution. Increasing the availability of native soil phospho-
rus and retarding the fixation or reversion of added phosphates are, therefore,
the problems of greatest scientific importance. These two phases will be dis-
cussed following a brief review of the phosphorus compounds present in soils.
10.4 Phosphorus Compounds in Soils3

Both inorganic and organic forms of phosphorus occur in soils and both are
important to plants as sources of this element. The relative amounts in the
two forms vary greatly from soil to soil but it is not at all uncommon for
more than half the phosphorus to be in the organic form. Data in Table 10.1
give some idea of their relative proportions in mineral soils. The organic fraction
3 For a review of soil phosphorus, see Larsen (1987).
10.4 Phosphorus Compounds in Soil 331

TABLE 10.1 Total Phosphorus Content of Soils from Different Areas and
the Percentage of Total Phosphorus in the Organic Forme
Number of Total P Organic

Soils samples (ppm) fraction ('JI.)
Western Oregon soils

Hill soils 4 357 66
Old valley-filling soils 4 1479 30
Recent valley soils 3 648 26
Iowa soils
Mollisols 2 613 42
Alfisols 2 574 37
Afisols 2 495 53
Arizona soils
Surface soils 19 703 36
Subsoils 5 125 34
Australia soils b
Spodosol 1 396 65
Vertisol 1 362 66
Mollisol 1 505 75
Ghana soilsc
Antoakrom site 1 32 55
Bofoyedru site 1 47 63
Somiabra site 1 64 70
Obuasi site 1 51 67
• Source for Oregon. Iowa. and Arizona is quoted by Brady (1974).

b Source for Australia is Fares et al. (1974).
c Source for Ghana is Acquaye (1963).
generally constitutes 20-80% of the total. Despite the variation that occurs, it
is evident that consideration of soil phosphorus would not be complete without
some attention to both forms (Figure 10.3).
Inorganic Compounds. Most inorganic phosphorus compounds in soils fall

into one of two groups: (a) those cont~ calci and (b) those containing
iron and aluminum. The ca cium compounds of most importance are listed
m Table 10.2 The apatite minerals are the most insoluble and unavailable of
the group. They may be found in even the more weathered soils, especially
in their lower horizons. This fact is an indication of the extreme insolubility
and consequent unavailability of the phosphorus contained therein. The simpler
gwounds calcium. suc as mono- and dicalcium phosphates. are readily
available for plant growth. Except on recently fertilized soils, however, these
t ompounds are present in extremely small quantities only because they easily
revert to the more insoluble forms.
Much less is known of the exact constitution of the iron and aluminum
phosphates contained in soils. The compounds involved are probably hydroxy
phosphates such as strengite and variscite, although these two chemicals exist
332 10 Supply and Avallability of Phosphorus and Potassium

Or------------------------,~777T.~7TTn777T.n77T----------~
Inorganic
20
40
E
~ 60
.
-5Q.
"C
'0
."
80
Residual Soluble in
100 dilute acid
120~----~----~----~----~~----L-----L-----~----~L---~
o 0.02 0.04 0.06 0.08
Soil phosphorus (%)
FIGURE 10.3 Distribution of phosphorus in organic and inorganic forms in an Iowa

soil. The dilute-acid-soluble inorganic phosphorus is more readily available than the
residual inorganic forms. In heavily fertilized soils the upper horizons would likely
be much higher in inorganic phosphorus. [From Black (1971).]
only in very acid soils. Hydroxy phosphates are most stable in acid soils and
are quite insoluble.
Many investigators have shown that phosphates react with certain iron
or aluminum silicate minerals such as kaolinite. There is some uncertainty,
however, as to the exact form in which this phosphorus is held in the soil.
Most evidence indicates that it, too, is probably fixed as iron or aluminum
phosphates, such as those described in the preceding paragraph.
Organic Phosphorus Compounds. There has been relatively less work done
on the organic phosphorus compounds in soils, even though this fraction often
comprises more than half of the total soil phosphorus. As a consequence, the
nature of most of the organic-bound phosphorus in soils is not known. However,
three main groups of organic phosphorus compounds found in plants are also
10.4 Phosphorus Compounds in Soil 333

TABLE 10.2 Inorganic Calcium Compounds
of Phosphorus Often Found in Soils
Listed in order of increasing solubility.
Compound Fonnula
Fluor apatite 3 Ca,(PO.h • CaF

Carbonate apatite 3 Ca, (PO.)2 • CaCO,
Hydroxyapatite 3 Ca, (PO.)2 • Ca(OHh
Oxyapatite 3 Ca,(PO.)2 • CaO
Tricalcium phosphate Ca3(PO.h
Octacalcium phosphate Ca,H2(PO.)•• 5H20
Dicalcium phosphate CaHPO.· 2H 20
Monocalcium phosphate Ca(H 2PO.)2
present in soils. These are a1 hytin and J.wJi!bderivatives, (b nucleic acids,

and (c phospholi ids. Wh' eo er organic phosphorus compounds are present
in soils, the identity and amounts present are not known.
Phytil). ~s a calcium-magnesium salt of phytic acid (inositol phosphoric
aci ,which has an empirical formula CH 6 H2PO')6' Phytin is the most abun-
dant of the known organic phosphorus compounds in soils, although it generally
accounts for no more than 30-40% of the total organic phosphorus. This com-
pound is quite insoluble in soils.
Phos hate is a cr'tic c onent of ribonucleic acid (RNA) and deoxyribo-
nu elC acid (DNA), which occur in all plant residues. They are also t ought
to be present in s ils, although at the relatively low levels of 1-2% of the
soil organic phosphorus. Phospholipids are phosphorus-containing fatty com-
pounds found in plants. They also make up only about 1-2% of the soil organic
phosphorus. Obviously, nearly two-thirds of the organic phosphorus is in forms
not as yet identified,
Phosphorus is present in h tin, nucleic acid and hospholipids in the
phosphate form. Consequent y, as microorganisms decompose these com-
pounds, the phosphate that is released is available to react with inorganic
compounds or to be taken up by plants.
10.5 Factors That Control the Availability of Inorganic

Soil Phosphorus
The availability of inorganic phosphorus is largely determined by (a) soil H;
lP soluble irolb aluminum. and manganese; (c) presence of iron-. alwmnum-.
an manganese-containing minerals ~ (d) availab e calcium and calcium miner-
als; (e) amount and decomposition of organic matter; and (f) activities of mi-
croorganisms. The first four factors are interrelated since soil pH drastically
influences the reaction of phosphorus with the different ions and minerals.

10.6 pH and Phosphate Ions
As indicated in Section 6.10, the availability of phosphorus to plants is deter-
mined to no small degree by the ionic form of this element (Figure 10.4). The
ionic form in turn is determined by the pH of the solution in which the ion
is found. Thus, in hi hI acid solutions only, H~ - ions are present. If the
pH is increased, first HP" .2- ions and finally P .3- ions dominate. This situation
is represented by the equation
OH- OH-
H 2PO.- ~ H 20 + HPO.2- ~ H 20 + PO.3-
(very acid H+ H+ (very alkaline
solutions) solution_)
At intermediate pH levels two of the phosphate ions may be present simultane-

ously. Thus, in solutions at pH 7.0, both H2PO.- and HPO.2- ions are found.
The H2 PO.- ion is somewhat more available to plants than is the HPO.2-
ion. In soils, however, this relationship is complicated by the presence or ab-
HP04~
......
"\
,- - -
I/
I \
I \
I \
I \
*- I \
c:
.g I
S \
E so
u
c:
o
I \
U I \
I \
I \
I \
I \
I \
I \
/. "-
o 2 4 6 8 10 12 14
pH of solution
FIGURE 10.4 Relationship between solution pH and the relative concentrations of

three soluble forms of phosphate. In the pH range common for soils, the H2PO.- ions
predominate.
10.6 pH and Phosphate IODS 335

sence of other compounds or ions. For example. the presence of soluble iron
and aluminum under very acid conditions. or calcium at high pH values. will
markedly affect the availability of the phosphorus. Clearly. therefore. the effect
of soil pH on phosphorus availability is determined in no small degree by
the various cations present. The effect of these ions in acid soils will be dis-
cussed first.
10.7 Inorganic Phosphorus Availability in Acid Soils

Assume that there is either a nutrient solution or an organic soil very low in
inorganic matter. Assume also that these media are acid in reaction but that
they are low in iron. aluminum. and manganese. The H2 PO, ions. which would
dominate under these conditions. would be readily available for plant growth.
Normal phosphate absorption by plants would be expected so long as the
pH was not too low.
Precipitation by Iron. Aluminum, and Manganese Ions. If the same degree

of acidity should exist in a normal mineral soil. however. quite different results
would be expected (Figure 10.5). Some soluble iron. aluminum. and manganese
100 .-------------------------------------------------------~
Relatively available phosphates
Fixation by
c: hydrous oxides of
.g 50 Fe, AI,and Mg Fixation m_ostly as
calcium phosphates
5'"
VI
o
Chemical
fixation by
O~ __ Fe,
soluble
~
AI. and Mn _ L_ _
__________ ~~_ _ _ _~_ _ _ _ _ _ _ _~_ _ _ _ _ _~~~_ _ _ _~
4.0 5.0 6.0 7.0 B.O

Soil pH
FIGURE 10.5 Inorganic fixation of added phosphates at various soil pH values.

Average conditions are postulated. and it is not to be inferred that any particular
soil would have exactly this distribution. The actual proportion remaining in an available
form will depend upon contact with the soil. time for reaction. and other factors. It
should be kept in mind that some of the added phosphorus may be changed to an
organic form in which it would be temporarily unavailable.

are usually found in strongly acid mineral soils. Reaction with the H 2PO.-
ions would immediately occur. rendering the phosphorus insoluble and also
unavailable for plant growth.
The chemical reactions occurring between the soluble iron and aluminum
and the H 2PO. - ions would result in the formation of hydroxy phosphates.
This may be represented as follows. using the aluminum cation as an example.
A13+ + H 2PO,- +
[soluble)
2 H 20 ;:::= 2 H+ + AI(OHhH2PO,
[insoluble)
Q
In most strongly acid soils the concentration of the iron and aluminum ions
•
greatly exceeds that of the H 2PO.- ions. Consequently. the above reaction
moves to the right. forming the insoluble phosphate. This leaves only minute
quantities of the H2PO. - ion immediately available for plants under these condi-
tions.
An interesting series of reactions occur when fertilizers containing
Ca(H2PO.h are added to soils. even those of relatively high pH (Lindsay and
Stephenson. 1959) (Figure 10.6). The Ca(H2PO.h in the fertilizer granules attracts
water from the soil and the following reaction occurs.
As more water is attracted. a H3PO.-laden solution with a pH of about 1.4

moves outward from the granule. This solution is sufficiently acid to dissolve
and displace large quantities of iron. aluminum. and manganese. These ions
react with the phosphate to form complex compounds. which later probably
revert to the hydroxy phosphates of iron. aluminum. and manganese in acid
soils and of calcium in neutral to alkaline soils. In any case. the immediate
products of the addition to soils of a water-soluble compound [Ca(H2PO.h'H20)
are a group of insoluble iron. aluminum. manganese. and calcium compounds.
Even so. the phosphorus in these compounds is released quite readily for plant
growth. It is only after these freshly precipitated compounds are allowed to
"age" or to revert to more insoluble forms that availability to plants is greatly
reduced.
Reaction with Hydrous Oxides. It should be emphasized that the H2PO.-

ion reacts not only with the soluble iron. aluminum. and manganese but also
with insoluble hydrous oxides of these elements. such as gibbsite (AI 20 3'3H20)
and goethite (Fe203·3H20). The actual quantity of phosphorus fixed by these
minerals in acid soils quite likely exceeds that due to chemical precipitation
by the soluble iron. aluminum. and manganese cations (Figure 10.5).
The compounds formed as a result of fixation by iron and aluminum oxides
are likely to be hydroxy phosphates. just as in the case of chemical precipitation
described above. Their formation can be illustrated by means of the following
10.7 Inorganic Phosphorus Availability in Acid Soils 337

X Ca(H 2 P0 4 h'H 2 0
• CaHP0 4 '2H 2 0
o H3 P04
+ Soluble Fe, AI, and Mn

@ Insoluble Fe, AI, and Mn
phosphates
- Direction of H2 0
movement
--. Direction of solution
movement
(a) (b)
(c) (d)
FIGURE 10.6 Reaction of Ca(H2PO,k H20 granules with moist soil. (a) The granule
has just been added to the soil and is beginning to absorb water from it. (b) In the
moistened granule H3PO, and CaHPO,' 2H2 0 are being formed, and H3PO, begins to
move out into the soil as more soil water is being absorbed. (c) The H,POdaden
solution moves into the soil. dissolving and displacing Fe. AI. and Mn and leaving
insoluble CaHPO,' 2H20 in the granule. (d) The Fe, AI, and Mn ions have reacted
with the phosphate to form insoluble compounds. which. along with the residue of
CaHPO,· 2H 20, are the primary reaction products. [Photos courtesy G. L. Terman and
National Plant Food Institute, Washington, DC}

equation if the hydrous oxide of aluminum is represented as aluminum hydrox-
ide.
OH OH
/ /
AI- OH + H2PO. - .,: AI- OH + OH-
"'- OH "'- H PO.
2
(soluble) (insoluble)
By means of this and similar reactions the formation of several basic phosphate
minerals containing either iron or aluminum or both is thought to occur. Since
several such compounds are possible. fixation of phosphorus by this mechanism
probably takes place over a relatively wide pH range. Also the large quantities
of hydrous iron and aluminum oxides present in most soils make possible
the fixation of extremely large amounts of phosphorus by this means.
Thus. as both of the equations above show. the acid condition that would
make possible the presence of the readily available H2 PO. - ion in mineral
soils at the same time results in conditions conducive to the vigorous fixation
or precipitation of the phosphorus by iron. aluminum. and manganese com-
pounds (Figure 10.6).
Fixation by Silicate Clays. A third means of fixation of phosphorus under

moderately acid conditions involves silicate minerals such as kaolinite. Al-
though there is some doubt about the actual mechanisms involved. the overall
effect is essentially the same as when phosphorus is fixed by simpler iron
and aluminum compounds. Some scientists visualize the fixation of phosphates
by silicate minerals as a surface reaction between exposed -OH groups on
the mineral crystal and the H2PO.- ions. Other investigators have evidence
that aluminum and iron ions. removed from the edges of the silicate crystals.
form hydroxy phosphates of the same general formula as those already dis-
cussed. This type of reaction might be expressed as follows.
[AI] + H2PO. - + 2 H20 .,: 2 H+ + AI(OHhH2PO.

(in silicate crystal) (insoluble)
Thus. even though phosphates react with different ions and compounds
in acid soils. apparently similar insoluble iron and aluminum compounds are
formed in each case. Major differences from soil to soil are probably due to
differences in rate of phosphate precipitation and in the surface area of the
phosphates once the reaction has occurred. This will be discussed again later.
Anion Exchange. The reactions described so far involved either the formation
of insoluble chemical precipitates or the replacement of OH groups on the
surface of either silicate clays or hydrous oxides. Phosphate can also participate
in simple anion exchange. As was pointed out in Chapter 5. certain positively
10.7 Inorganic Phosphorus Availability in Acid Soils 339

charged colloidal particles are the seat of exchange between two anions. This
can be illustrated with "-AIOH + to represent the positively charged particle.

2
/
[~AIOHZ+ ] OH + HzPO.- ~ [~AIOHZ+ ]H2PO. + OH-

positively positively
charged particle charged particle
Note that the reaction is reversible; that is. the OH- ion can replace the H 2 PO.-
ion and remove it from the colloidal surface to the soil solution. This reaction
shows how anion exchange takes place and illustrates the importance of liming
acid soils in helping to maintain a higher level of available phosphorus.
10.8 Inorganic Phosphorus Availability at High

pH Values
The availability of phosphorus in alkaline soils is determined largely by the
solubility of the calcium compounds in which the phosphorus is found. If an
H2PO. - -containing fertilizer such as concentrated superphosphate is added
to an alkaline soil (say at pH = 8.0). the H 2PO,- ion quickly reacts to form
less soluble compounds. Three such compounds are dicalcium phosphate dihy-
drate (DCPD). CaHPO,'2H2 0; octacalcium phosphate (OCP). CaSH2 (PO,)a-5H20;
and tricalcium phosphate (TCP). Ca3(PO,h. While the specific mechanisms
for the formation of these compounds are not well established. their relationship
to each other can be shown rather simply.
Ca(H2PO,h + CaC03 + H20 --+ 2 CaHPO, . 2H20 + CO 2

DCPD
6 CaHPO,· 2HzO + 2 CaC03 + H20 - Ca.Hz(PO.)e- 5H20 + 2 CO 2

DCPD OCP
Ca.H2(PO.),· 5H20 + CaC03 - 3 Ca3(PO.h + CO 2 + 6 H20

OCP TCP
The solubility of the compounds and. in turn. the availability to plants

of the phosphorus they contain decrease as the phosphorus changes from the
H2PO, - ion to the DCPD and finally to the TCP.
Although the Ca3(PO.h (TCP) thus formed is quite insoluble. it may be
converted in the soil to even more insoluble compounds. Hydroxy. oxy. carbon-
ate. and even fluor apatite compounds may be formed if conditions are favora-
ble and if sufficient time is allowed (Table 10.2).
This type of reversion may occur in soils of the eastern United States

which have been heavily limed. It is much more serious, however, in western
soils, owing to the widespread presence of excess CaCO s. The problem of
utilizing phosphates in alkaline soils of the arid West is thus fully as serious
as it is on highly acid soils in the East.
10.9 pH for Maximum Inorganic Phosphorus

Availability
With insolubility of phosphorus occurring at both extremes of the soil pH
range (Figure 10.5), the question arises as to the range in soil reaction in which
minimum fixation occurs. The basic iron and aluminum ~hosphates have a
minimum solubility around pH 3-4. At higher pH values some of the phosphorus
IS released and the fixing capacity somewhat reduced. Even at pH 6.5, however,
much of the phosphorus is still probably chemically combined with iron and
a uminum. As the pH approaches 6, precipitation as calcium compounds begins;
at pH 6.5 the formation of insoluble calcium salts is a factor in rendering the
phosphorus unavailable. Above pH 7.0, even more insoluble compounds, such
as apatites, are formed.
These facts seem to indicate that maximum phosphate availability to plants
is 0 ained when the soil pH is maintained in the 6.0-7.0 range (Figure 10.5).
Even in this range, however, the fact should be emphasized that phosphate
availability may still be very low and that added soluble phosphates are readily
fixed by soils. The low recovery (perhaps 10-30%) by plants of added phos-
phates in a given season is partially due to this fixation.
10.10 Availability and Surface Area of Phosphates

When soluble phosphates are added to soils, two kinds of compounds form
immediately: (a) fresh precipitates of calcium phosphate or iron and aluminum
phosphates and (b) similar compounds formed on the surfaces of either calcium
carbonate or iron and aluminum oxide particles. In each case, the total surface
area of the phosphate-held particles is high, and consequently the ease of
availability of the phosphorus is reasonably great. Thus, even though the water-
soluble phosphorus in superphosphate may be precipitated in the soil in a
matter of a few days, the freshly precipitated compounds will release much
of their phosphorus to growing plants.
Effects of Aging. With time, changes take place in the reaction products of
soluble phosphates and soils. These changes generally result in a reduction
in surface area of the phosphates and a similar reduction in their availability.
An increase in the crystal size of precipitated phosphates occurs in time. This
decreases tJteir surface area. Also, there is a penetration of the phosphorus
held by calcium carbonate and iron or aluminum oxide particles into the particle
10.10 AvailabiUty and Surface Area of Phosphates 341

(a) (b) (c)
FIGURE 10.7 How relatively soluble phosphates are rendered unavailable by

compounds such as hydrous oxide. (a) The situation just after application of a soluble
phosphate. The root hair and the hydrous iron oxide particle are surrounded by soluble
phosphates. (b) Within a very short time most of the soluble phosphate has reacted
with the surface of the iron oxide crystal. The phosphorus is still fairly readily available
to the plant roots since most of it is located at the surface of the particle where exudates
from the plant can encourage exchange. (c) In time the phosphorus penetrates the
crystal and only a small portion is found near the surface. Under these conditions its
availability is low.
itself (Figure 10.7). This leaves less of the phosphorus near the surface where
it can be made available to growing plants. By these processes of aging, phos-
phate availability is reduced. Thus, the supply of available phosphorus to plants
is determined not only by the kinds of compounds that form but also by their
surface areas (Figure 10.8).
FIGURE 10.8 The effect of clay 70

content on the percent recovery of
fertilizer phosphorus by seven crops
grown on four calcareous soils. Soils ~ 65
with higher clay contents tended to 2
u
fix the phosphorus in forms not readily >-
.D
available to the crop plants. [From '"
:J
Olsen et al. (1977); used with 5 60
.<:
pennission of the World Phosphate 0.
'"
o
Industry Association, Paris, France.} .<:
0.
1::
-c 55
-c
....'"o
t-
~ 50
~
.
u
10 20 30 40 50 60
Soil clay (%)

Relation to Soil Texture. Most of the compounds with which phosphorus re-
acts are in the finer soil fractions. As a consequence phosphorus fixation tends
to be more pronounced in clay soils than in tlie coarser-textured ones. This
act is borne out by the data in Figure 10.8, which clearly illustrates the tendency
of clays to reduce phosphate avaiiability.
10.11 Phosphorus-Fixing Power of Soils

In light of the above discussion it is interesting to note the actual quantities
of phosphorus that soils are capable of fixing. Data from three New Jersey
soils presented in Table 10.3 emphasize the tremendous power of certain soils
in this respect. For example, to satisfy the phosphorus-fixing power of the
unlimed Collington soil, nearly 105 Mg of ordinary superphosphate containing
10% P would be required. Although liI!!!Pg definitely reduced the fixing capacity,
the quantity of phosphorus fixed even on the limed soils is enormous. Thus,
over 56 Mg of superphosphate would be required to satisfy completely the
phosphorus-fixing power of a hectare-furrow slice of the limed Collington soil.
TABLE 10.3 Phosphorus-Adsorbing Power of Three

New Jersey Soils Limed and Unlimeda (upper 15 em)
Phosphorus
fixing power (P)
Soil Treatment pH kg/ha Ih/A
Sassafras No lime 3.6 2780 2480

Sassafras Lime 6.5 1361 1215
Collington No lime 3.2 9173 6184
Collington Lime 6.5 4920 4390
Dutchess No lime 3.8 6727 6002
Dutchess Lime 6.5 4309 3844
• From Toth and Bear (1947).
10.12 Influence of Soil Organisms and Organic Matter

on the Availability of Inorganic Phosphorus
In addition to pH and related factors, organic matter and microorganisms strik-
ingly affect inorganic phosphorus availability. Just as was the case with nitro-
gen, the rapid decomposition of organic matter and consequent high microbial
population result in the temporary tying up of inorganic phospha tes in microbial
tissue.
Products of organic decay such as organic acids and humus are thought
10.12 InBuenee of Soil Organisms and Organie Matter 343

FIGURE 10.9 The effect of added
organic matter (manure) on the
soluble phosphorus level of soil at pH 70
7.2. As the manure decomposed.
organic acids were rele~sed that
formed stable complexes with iron
and aluminum compounds and also 60
affected the' solubility of calcium
phosphates. [Data from EI-Baruni and
Olsen (1979).]
50
e-o.
..:;
<II
~
15 40
.<:
a.
<II
o
.<:
a.
.!!
.D
~ 30
(5
Vl
20
10
OL-________L -______ ~ __________________ ~
o 11 22 44
Manure added (tons/ha)
to be effective in forming complexes with iron and aluminum compounds. This

engagement of iron and aluminum reduces inorganic phosphate fixation to a
remarkable degree. Figure 10.9 shows the effect of manure application on the
soluble phosphorus level in soils. Apparently the manure was effective in re-
leasing phosphorus after it had been fixed as Fe. Al. and Ca phosphates. Thus.
organic decomposition products undoubtedly play an important role in inor-
ganic phosphorus availability.
10.13 Availability of Organic Phosphorus

Only meager information has been obtained on the factors affecting the availa-
bility to higher plants of organic phosphorus compounds. Even though both
phytin and nucleic acids can be utilized as sources of phosphorus. ino anic
sources of this element are needed for normal production. Plants commoiily
suffer from a phosphorus deficiency even in the presence of considerable quanti-

ties of organic forms of this element. Just as with inorganic phosphates. the
problem is one of availability.
Phytin behaves in the soil much as do the inorganic phosphates. forming
iron. aluminum. and calcium phytates. In acid soils the phytin is rendered
insoluble and thus unavailable because of reaction with iron and aluminum.
Under alkaline conditions calcium phytate is precipitated and its phosphorus
is rendered unavailable.
The fixation of nucleic acids involves an entirely different mechanism.
but the end result-low phosphorus availability-is the same. Evidently. nucleic
acids are strongly adsorbed by clays. especially montmorillonite.
This adsorption is particularly pronounced under acid conditions and re-
sults in a marked decrease in the rate of decomposition of the nucleic acids.
Consequently. the available phosphorus supply from this source is low. espe-
cially in acid soils which contain appreciable amounts of montmorillonite.
The judicious application of lime to acid soils is thus fully as important
in organic phosphorus nutrition as it is in rendering inorganic compounds avail-
able. Whether we are dealing with inorganic soil phosphates. added fertilizers.
or organic materials. the importance of lime as a controlling factor in phosphate
availability is clearly evident.
10.14 Intensity and Quantity Factors

It is important to be aware of the different forms in which phosphorus is found
in soils. But it is even more important to know a soil's ability to maintain
sufficiently high levels of phosphorus in the soil solution to assure satisfactory
plant growth. The concentration of phosphorus in the soil solution is a measure
of the intensity 7actor of phospHorus nutrition. If this factor is maintained
at about 0.2 ppm or above. maximum yield of most crop plants will occur
(Table 10.4).
TABLE 10.4 Concentration of Phosphorus
in Soil Solution That Provided 95% of
Maximum Yield of Several Crops in Hawaii-
Approximate P in
IOU lolution
Crop SoU (ppm)
Cassava Halii 0.005

Peanut Halil 0.01
Com Halii 0.05
Soybean Halil 0.20
Cabbage Kula 0.04
Tomato Kula 0.20
Head lettuce Kula 0.30
• From Fox (1981).
10.14 Intensity and Quantity Factors 345

As plant roots take up phosphorus from the soil solution. it is at
least
partially replenished by release of phosphorus from the labile forms.
the soil
solids that are in equilibrium with the soil solution. This source of soil
solution
replenishment is known as the 'LU1nUl-y-{ Q} factor of phosRhorus
nutrition.
While it involves all solid forms of phosphorus that release s this elemen
t to
the solution. it is made up primarily of the slowly available forms
shown in
Read il y available phosphat es

- (soil solution)
H2 P0 4 - and HP0 4 2 - io ns rel eased from other forms or added in
fertili zers
Slowly available phospha tes

(labile)
Fe, AI, and Mn phospha tes (acid soils) and Ca and Mg phospha tes
(alkal ine so ils)
that have been freshly precipita ted or are held mostly on the surface
of fine
particles in the soil
Very slowly available phosphat es

(non labile)
Precipita tes of Fe, AI, Mn, Ca, and Mg phospha tes that have aged
and are well crystall ized .
Phospha tes that were held on particle surfaces have penetrate d the
particl es, little rema in-
ing on the su rface. Also includes stable organic phosphat es.
FIGUR E 10.10 Classification of phosphorus compounds in soils in three

major groups.
Fertilizer phosphates are generally in the readily available phosph ate
(soil solution)
group, but are quickly converted to the slowly available (labile) forms.
These can be
utilized by plants at first, but upon aging are rendered less availab le
and are then
classed as very slowly available (nonlabile). At anyone time perhaps
80-90% of the
soil phosphorus is in very slowly available forms. Most of the remain
der is in the
slowly available form since perhaps less than 1% would be expecte
d to be readily
available. Note that phosphorus moves from one form to another althoug
h the movement
is slow.

Figure 10.10. They are freshly precipitated Fe, AI, Mn, and Ca compounds
and surface-adsorbed phosphates that have not yet penetrated the particles
on which they are held.
As shown in Figure 10.11, the Q level needed to provide a given intensity
(I) or soil solution phosphorus level will vary from soil to soil. Tropical clays
high in Fe and Al need a high Q level to assure an I level sufficient for normal
growth. In contrast sandy soils with low clay and Fe and Al contents provide
higher intensities with a given quantity of phosphorus.
When plant roots remove a given quantity of phosphorus from the soil
solution (reduce the I factor), the level of I is drastically reduced in the sandy
soil and may be reduced only slightly in the clay soil. The latter is thus said
to be more highly buffered with respect to phosphorus than the sandy soil.
The otential buffering capacity (PBC of a soil is given by
PBC=~Q
~l
-;;;-
E
.2
~ Qs
.0
~
c:
Q..
0'
'E
c:
"'
:::I
0'
QA
11
Intensi ty.I (P in sol ution) Intensity, I (P in solution)
(a) (b)
FIGURE 10.11 Relationship between the intensity factor (P in solution) and the
quantity factor (P in solid labile forms that are in equilibrium with P in solution) on
two soils. Soil A may be a sandy soil low in phosphorus-binding compounds. while
soil B is a heavier-textured soil high in Fe. AI. Mn. or Ca that holds the phosphorus
in relatively unavailable forms. (a) To provide a given level of P in the soil sorution
(intensity) a much higher quantity must be present in soil B than in soil A. (b) However,
when a given quantity (~Q) of phosphorus is removed from the soil by a crop. the
decrease in intensity is much greater for soil A (~h) than for soil B (Ma). Soil B is
more highly buffered than soil A.

aQ is the change in the quantity (Q factor). and al is the change in the
intensity (I factor).
The quantity/intensity relations of phosphorus in soils and the potential
buffering capacity are important in determining the fertilizer phosphate require-
ments for high yields. We shall see in Section 10.22 that this same general
relationship holds for potassium.
10.15 Practical Control of Phosphorus Availability

From a practical standpoint. the phosphorus-utilization picture is not too en-
couraging. The inefficient utilization of applied phosphates by plants has locg
been known. Most crops do not take up more than about 10-15% of the phospho-
rus added in fertilizers during the year the fertilizer is applied. This is due
not only to the tendency of the soil to fix the added phosphorus but to the
slow rate of movement of this element to plant roots in the soil.
Continuing application of phosphate fertilizers in time tends to increase
the level of this nutrient in the soil and particularly its level in the labile
forms which can release phosphorus to the soil solution. Thus. even though
much of the phosphorus added in fertilizer is not used during the year of
application. it may provide an important source in future years.
Liming and Placement of Fertilizers. The small amount of control that can
be exerted over phosphate availability seems to be associated with liming,
fertilizer placement, and organic matter maintenance. By holding the pH of
soils between 6.0 and 7.0, the phosphate fixation can be kept at a minimum
(Figure 10.5). To prevent rapid reaction of phosphate fertilizers with the soil,
these materials are commonly placed in localized bands. In addition, phosphatic
fertilizers are quite often granulated to retard still more their contact with
the soil. The effective utilization of phosphorus in combination with animal
FIGURE 10.12 How the available Crop resid ues Commercial Phosphorus-bearing
phosphorus level in a soil is depleted Manures fertilizers soil minerals "
,,
/
and replenished. Note that the two
main features are the addition of \
phosphate fertilizers and the fixation \
of this element in insoluble forms. \
It should be remembered that the Soil organic--.....~ Available soil I
matter phosphorus I
amount of available phosphorus in
I
the soil at anyone time is relatively /
small, especially when compared to /
those of calcium. magnesium. and /
/
potassium. /
Crop Leaching Erosion Fixation --./
removal losses losses
348 10 Supply and AvailabUity of Phosphorus and Potassium

manures is evidence of the importance of organic matter in increasing the
availability of this element.
In spite of these precautions. a major portion of the added phosphates
still reverts to less available forms (Figure 10.12). It should be remembered.
however. that the reverted phosphorus is not lost from the soil and through
the years is slowly made available to growing plants. This becomes an impor-
tant factor. especially in soils that have been heavily phosphated for years.
In summary. maintaining sufficient available phosphorus in a soil largely
narrows down to a twofold program: (a) the addition of phosphorus-containing
fertilizers and (b) the regulation in some degree of the fixation in the soil of
both the added and the native phosphates.
10.16 Potassium-The Third "Fertilizer" Element

The history of fertilizer usage in the United States shows that nitrogen and
phosphorus received most of the attention when commercial fertilizers first
appeared on the market. Although the role played by potassium in plant nutri-
tion has long been known. the importance of potash fertilization has received
full recognition only in comparatively recent years.
The reasons that a widespread deficiency of this element did not develop
earlier are at least twofold. First. the supl'l of available potassium originally
was so high in most soils that it oOK many' y':ears of cropping for a serious
depletion to appear. Second. eve thougll, the potassium in certain soils may
have been insufficient for optimum crop yields. production was much more
drastically limited by a lack of nitrogen and phosphorus. With an increased
usage of fertilizers carrying these latter elements. crop yields have been corre-
spondingly increased. As a consequence. the drain on soil potassium has been
greatly increased. This. coupled with considerable loss by leaching. has en-
hanced the demand for potassium in commercial fertilizers.
10.17 Effects of Potassium on Plant Growth5

Potassium plays many essential roles in plants. It is an activator of dozens
of en~ymes responsible for such plant processes as energy metaliolism. starch
synthesis. nitrate reduction. and sugar degradation. Because of its ease oftrans-
port across plant membranes. it is extremely mobile within the plant. Its rela-
tively high concentration in plant cells helps it regulate the opening and closing
of stomates in the leaves and the uptake of water by root cells.
Potassium is essential for photosynthesis and for starch formation and
the ranslocation of sugars. It is necessary in the development of chlorophyll.
although it does not. like magnesium. enter prominently into its molecular
5 For further information on this topic see Mengel and Kirby (1980) and Sekhon (1978).
10.17 Effects of Potassium on Plant Growth 349

structure. This element is important to cereals in grain formation,
as it aids
in the deve opment of plump, heavy kernels. Abund ant available
potass ium
also is absolutely necessary for tuber development. Therefore, the percen
tage
of this element usually is comparatively high in mixed fertilizers recomm
ended
for potato es. All root coops respon d to liberal applications of potass
ium. As
with phosphorus, it may be presen t in large quantities in the soil
and yet
exert no harmful e ect on the crop.
By increasing crop resistance to certain diseases and by encouraging strong
root and stem systems, potassium tends to prevent the undesirable
"lodging"
of plants and to counteract the damaging effects of excessive nitrogen.
In delay-
ing maturity, potassium works agains t undue rip'ening influences of phosph
orus.
In a general way, it exerts a balancing effect on both nitrogen and phosph
orus,
and consequently IS especially important in a mixed fertilizer.
In considering potassium plant nutrition it should be noted that sodium
has been found to partially take the place of potassium in the nutritio
n of
certain plants. When there is a deficiency of potash, the native sodium
of
the soil, or that added in such fertilizers as nitrate of soda, may be very
useful.
10.18 The Potassium Cycle

Figure 10.13 shows the major forms in which potassium is held in
soils and
the changes it undergoes as it is cycled through the soil and plant
systems.
The original sources of potassium are the primary minerals such as
the micas
and potash feldspar (microcline). As these minerals weather, their rigid
lattice
structures become more pliable. Potassium held betwee n their 2:1-typ
e layers
is slowly made more available, first through nonexchangeable but slowly
avail-
able forms, and finally through the readily exchangeable and the soil
solution
forms from which plant roots take up this element. At anyon e time
most of
the potassium is in the primary mineral and nonexchangeable forms.
But the
exchangeable and soil solution potassium are the forms of greates t immed
iate
concern to plant growth. To mainta in the levels of these last two forms
high
enough to encourage good crop production, it has become increasingly
neces-
sary to supplement soil-borne potassium with applications of chemic
al fertil-
izer. The sections that follow give greate r details on the reactions
involved
in the potassium cycle.
10.19 The Potassium Problem

Availability of Potassium. In contra st to the situation regarding phosph
orus,
most mineral soils, except those of a sandy nature, are comparativel
y high
in total potassium. In fact, the total quantity of this element is generally
greater
than that of any other major nutrient element. Amounts as great as
35,000-
55,000 kg potassium per hectar e-furro w slice (31,225-44,600 lb per acre-fu
rrow
350 10 Supply and Availability of Phospborus and Potassium
~
Chemical
fertilizers
~,o;""~.d;'l'''''"'·-'''.''~;''''''
n ... ~"lO .. llll:~'\oO; ".".'~ •. .r.y...;;;."':".... "'~';'
Microbial
tissue
~
~
~
(""d)
~(","Od"Y mio,rnl,)
No",,,h,o.,,bI, K
ExchangeableK ~ ~~
~==:::..~ Primary soil minerals

(micas, feldspars, etc.)
fiGURE 10.13 The major components of the potassium cycle. Primarily soil minerals
such as the micas and feldspars are the original sources of potassium. They weather
to fine micas (illite) and other silicate clays in which some of the potassium is held
in a nonexchangeable. but slowly available form. The nonexchangeable potassium is
slowly released to the exchangeable form and later to the soil solution, from which it
is absorbed by plant roots, and is eventually recycled through plant residues and wastes
to the soil. At anyone time, most of the potassium is in primary minerals or in the
nonexchangeable or fixed form. Chemical fertilizers are increasingly important sources
of potassium.
slice) are not at all uncommon (see Table 1.3). Yet the uantit~ of potassium
held in an easily exchangeable condition at anyone ime often is very smarr.
Most of this element is held rigidly as part of the primary minerals or is fixed
in forms that are at best only moderately available to plants. Also competition
by microorganisms for this element contributes at least temporarily to its una-
10.19 The Potassium Problem 351

vailability to higher plants. Thus. the situati on in respec t to potass ium
utiliza-
tion paralle ls that of phosphorus and nitrogen in at least one way.
A very
large proportion of all three of these elements in the soil is insolub
le and
relatively unavailable to growing plants.
Leaching Losses. Unlike the situati on with respect to phosphorus.

howev er.
mJl_ch I'otassium is lost by leaching. An examin ation of the draina
ge water
from mineral soils on which rather liberal fertilizer applica tions
have been
made will usually show considerable quantities of potassium. In extrem
e cases.
the magnitude of this loss may approa ch that of potass ium remov
al by the
crop. For example. heavily fertilized sandy soils on which crops such
as vegeta-
bles or tobacco are grown may suffer serious losses by leaching.
Even on a
representative humid region soil receiving only moder ate rates of
fertilizer.
the annual loss of potass ium by leaching is usually about 35 kg/ha
(31 Ib/ A)
(see Table 15.7).
Crop Removal. The third phase of the potassium problem concerns

the quan-
tity of this element in plants -in other words. its removal by growin
g crops.
Under ordina ry field conditions and with an adequa te nutrien t supply
. potas-
sium removal by crops is high. often being three to four times that of phosph
orus
and equaling that of nitrogen. The removal of 120-15 0 kg/ha (107-13
4 Ib/ A)
of potassium by a 50 Mg/ha silage com crop is not at all unusual.
Moreover. this situation is made even more critical by the fact that
plants
tend to take up soluble potassium far in excess of their needs if sufficie
ntly
large quantities are present. This tenden cy is termed lux consumption, be-
cause the excess potassium absorb ed appare ntly does not increas e crop
yields
to arW extent.
Examples of Luxury Consumption. The principles involved in luxury

con-
sumption are shown by the graph of Figure 10.14. For many crops
there is a
more or less direct relationship betwee n the available potassium
in the soil
and the removal of this element by plants. The availab le potassium
would.
of course. include both that added and that already present. A certain
amoun t
of this element is needed for optimum yields and this is termed require
d potas-
sium. All potassium above this critical level is considered a luxury, the remov
al
of which is decidedly wasteful.
Under field conditions. luxury consumption becomes particularly wastef
ul.
For example. to save labor. one may be tempted to supply potassi
um only
during the first year of a three- or four-year perennial hay crop. Much
of the
potassium thus added is likely to be absorb ed wastefully by the first
crop of
hay or even in the first cutting. Consequently. too little of the added
potass ium
would remain for subseq uent crops.
In summary. then. the problem of potassium economy in its most genera
l
terms is at least threefold: (a) a very large proportion of this elemen
t at a
given time is relatively unavailable to higher plants; (b) becaus e of the
solubility
------ ------ ----.
High r----- ------ ------ ------ ------ ------
Potassium
content
.'!l
c of plants ~
to
C.
.....
...oc Luxury
--- --------:]~---
'"
C
ou
E
:::I
.~
o
0..
~ Potassium required for
optimum growth
_____ ___
_____ _____ _____ _____ _____ _____ _____ _____
~
Low~
High
Low
Potassium available in soil
of plants and
FIGUR E 10.14 General relationship betwee n the potassium content
rs are applied to a
the available soil potassium. If excess quantities of potash fertilize
of that require d for optimum yields.
soil. the plants will absorb potassium in excess
be wastefu l, especia lly if the crops are comple tely
This luxury consumption may
removed from the soil.
and
of its available forms. potassium is subject to wasteful leaching losses;
high. especia lly when luxury
(c) the removal of potassium by crop plants is
ound.
quantities of this element are supplied. With these ideas as a backgr
availab ilities will now be
the various forms of potassium in soils and their
considered.
10.20 Forms and Availability of Potas sium in Soils

ied on
For convenience. the various forms of potassium in soils can be classif
groups : (a) navail J
abl J, (b) readily
the basis of availability in three general
ium is
ayailable and (c) slowly availa blel Although most of the soil potass
an immed iate practic al standp oint the
in the first of these three forms. from
latter two are undoubtedly of greate r signific ance.
-
The relationship among these three general categories is shown diagram
tenden cies presen ted therein are of vital
matically in Figure 10.15. Equilibrium
avail-
practical importance. especially when dealing with the slowly and readily
one form to anothe r can and does occur.
able forms. A slow change from
10.20 Forms and Availability of Potassium in sons 353

Relatively unavailable potassium
(feldspars, micas, etc.)
Slowly available potassium

, 90- 98% of total potassium
J
Readily available potas ium
(nonexch angeable = fixed)
(exchang eable and in soil solution )
1-10% of total potassium
1- 2% of total potassium
\
I
~
'-y-J
Nonexch angeable K
FIGUR E 10.15 Relative proportions of the total soil potassi um in unavail

able, slowly
available, and readily availab le forms. Only 1-2% is rated as readily
available. Of
this, approximately 90% is exchangeable and only 10% appears in the
soil solution at
any time. [Modified from Attoe and Truog (1945).]
This makes possible a fixation and conservation of added soluble potass

ium
and a subsequent slow release of this element when the readily
availab le
supply is reduced.
Relatively Unavailable Forms. B far the greates t part (perhaps 90-98%

) of
all soil potassium in a mineral sOlI IS in relatively unavailable forms
(Figure
0.15). The compounds containing most of this form of potassium
are the feld-
spars and the micas. These minerals are quite resista nt to weathe
ring and
probably supply relatively insignificant quantities of potassium during
a given
growing season. However, their cumulative contribution over a period
of years
to the overall available potassium in the soil undoubtedly is of consid
erable
importance. Potassium is gradually release d to more available forms
through
the action of solvents such as carbon ated water. Also. the presence
of acid
clay is of some significance in the breakd own of these primary minera
ls with
the subsequent release of potassium and other bases (see Section 12.4).
Readily Available Forms. The readily available potassium constit

utes only
about 1-2% of the total amount of this element in an average minera
l soil. It
exists in soils in two forms: (a) potassium in the soil solution and (b) exchan
gea-
ble potassium adsorb ed on the soil colloidal surfaces. Although most
of this
available potassium is in the exchangeable form (approximately 90%).
soil
solution potassium is most readily absorb ed by higher plants and is. of
course,
subject to considerable leaching loss.

As represented in Figure 10.15. these two forms of readily available potas-
sium are in dynamic equilibrium. Such a situation is extremely important from
a practical standpoint. In the first place. absorption of soil solution potassium
by plants results in a temporary disruption of the equilibrium. Then to restore
the balance! some of the exchangeable potassium immediately moves into
the soil solution until the equilibrium is again established. On the other hand.
when water-soluble fertilizers are added. the reverse of the above adjustment
occurs. The exchangeable potassium can be seen as an important buffer mecha-
nism for soil solution potassium.
Slowly Available Forms. In the presence of vermiculite. smectite. and other
2:1-type minerals the potassium of such fertilizers as muriate of potash not
only becomes adsorbed but also may become definitely "fixed" by the soil
colloids (Figure 10.16). The potassium as well as ammonium ions fit in between
layers in the crystals of these normally expanding clays and become an integral
part of the crystal. Potassium in this form cannot be replaced by ordinary
exchange methods and consequently is referred to as nonexchangeable potas-
sium. As such. this element is not readily available to higher plants. This
form is in equilibrium. however. with the available forms and consequently
acts as an extremely important reservoir of slowly available potassium. The
entire equilibrium may be represented as follows.
Nonexchangeable K -=
slow rapid..
Exchangeable K ;= SOlI soluhon K
L =-= :::..::;:-:=
I I
-.
(8) Mica Hydrous micas (e.g., illite) (b) Vermiculite

CEC = 0 CEC = 15.-40 =
CEC 150
• Potassium ion, dehydrated @80 Exchangeable cations, hydrated

FIGURE 10.16 Diagrams to illustrate the release of potassium from primary micas
to fine-grained mica (illite) and then to vermiculite and the fixation of exchangeable
potassium by reversing these release reactions. Note that the dehydrated K+ ion is
much smaller than the hydrated ions of Na+, Ca 2 +, Mg2+, etc. Thus, when potassium
is added to a soil containing 2:1-type minerals such as vermiculite, the reaction may
go to the left and K+ ions are held tightly (fixed) in between layers within the crystal,
giving an illite-type structure. [Modified from McLean (1978); used with permission of
Potash Research Institute of India.}
10.20 Forms and Availability of Potassium in Soils 355
TABLE 10.5 Potassium Removal by Very Intensive Cropping and the
Amount of This Element Coming from the Nonexchangeable Form
Total K used by Peroent

cropll derived from
nonexchangeable
SoU kg/ha Ib/A form
Wisconsin soils o
Carrington silt loam 133 119 75
Spencer silt loam 66 59 80
Plainfield sand 99 88 25
Mississippi soils b
Robinsonville fine silty loam 121 108 33
Houston clay 64 57 47
Ruston sandy loam 47 42 24
o Average of six consecutive cuttings of Ladino clover, from Evans and Attoe
(1948).
" Average of eight consecutive crops of millet, from Gholston and Hoover
(1948).
The importance of this adjustment to practical agriculture should not be

overlooked. It is of special value in the conservation of added potassium. For
example. when potassium-containing fertilizers are added to the soil. a large
proportion of the soluble (soil solution) potassium becomes attached to the
colloids. As a result. the above equilibrium shifts to the left. and some exchange-
able ions are converted to the nonexchangeable form. Although this potassium
is at least temporarily unavailable. it is not subject to leaching and thus a
significant conservation is attained. Also. since the fixed potassium is slowly
reconverted to the available forms later. it is by no means completely lost to
growing plants.
Release of Fixed Potassium. The above reaction is perhaps of even greater
practical importance in another way. The quantity of nonexchangeable or
"fixed" potassium in some soils is quite large. The fixed potassium in such
soils is continually released to the exchangeable form in amounts large enough
to be of great practical importance. The data in Table 10.5 indicates the magni-
tude of the release of nonexchangeable potassium from certain soils. In several
cases cited. the potassium removed by crops was supplied largely from nonex-
changeable forms.
10.21 Factors Affecting Potassium Fixation in Soils

Several soil conditions markedly influence the amounts of potassium fixed.
Among the factors are (a) the nature of the soil colloids. (b) wetting and drying.
(c) freezing and thawing. and (d) the presence of excess lime.

Effects of Type of Clay, Moisture, and Temperature. The ability of the various
soil colloids to fix potassium varies widely. For example, l:l-type clays suc
as kaolinite and soils in which these clay minerals are ominant fix little
potassium. On the other hand, clays of the 2:1 type, such as vermiculite, smec-
fite, and fine-grained mica (illite), fix potassium very readily and in large
amounts. Even silt-sized fractions of some micaceous minerals fix and subse-
quently release potassium.
The potassium and ammonium ions are attracted between layers in the
clay crystals by the same negative charges responsible for the internal adsorp-
tion of these and other cations. The tendency for fixation is greatest in minerals
where the major source of negative charge is in the silica (tetrahedral) sheet.
Thus vermiculite has a greater fixing capacity than montmorillonite (see Table
5.4 for formulas for these minerals).
The mechanism for potassium fixation may vary somewhat from one clay
mineral to another. In the case of illite and some smectites and vermiculites,
the potassium ions may penetrate the crystal lattice and be trapped when
the layers contract during periods of drying. Clay minerals with a high negative
charge caused by the Al3+-for-SiH substitution (see Section 5.7) will strongly
bind the K+ ion and prevent its being exchanged. Some weathered micas may
simply permit the K+ ions to reenter the surface potassium sites that were
vacated when the mineral weathered. It is easy to see why there would be
such wide variability in the K-fixing capacity of clays.
The mechanism for potassium fixation is probably the same as that for
fixation of the ammonium ion. These two ions do not have as high an affinity
for water of hydration as do other cations such as Na+ and Ca 2+. As a conse-
quence, they can easily be dehydrated, and then their small size is such as
to permit them to fit snugly between the silica sheets of adjoining layers in
2: I-type clay minerals (Figure 10.16). Once in place, these ions become trapped
as a part of the rigid crystal structure, thereby preventing normal crystal lattice
expansion and reducing the cation exchange capacity of the clay. The larger
hydrated ions of cations such as Na+, Ca2+ and Mg2+ are not able to fit between
these layers and consequently escape fixation.
Alternate wetting and drying, and freezing and thawing has been shown
to result in the fixation of potassium in nonexchangeable forms as well as
its ultimate release to the soil solution. Although the practical importance of
this is recognized, its mechanism is not well understood.
Influence of Lime. Applications of lime sometimes result in an increase in

potassium fixation of soils (Figure 10.17). Under normal liming conditions this
may be more beneficial than detrimental because of the conservation of the
potassium so affected. Thus, potassium in well-limed soils is not as likely to
be leached out as drastically as is that in acid soils.
There are conditions, however, under which the effects of lime on the
availability of potash are undesirable. For example, in soils where the negative
charge is pH-dependent liming can greatly reduce the level of potassium in
10.21 Factors Affecting Potassium Fixation in Soils 357

30
24
~
c:
,g
'"
)(
;.;:; 18
E
:::I
';;;
VI
'0'"
0..
12
3 4 5 6 7 8 9 10
pH
FIGURE 10.17 The effect of pH on the fixation of potassium in Indian soils. [From
Grewal and Kanwar (1976); used with permission of Indian Council of Agricultural
Research ·1
the soil solution (Figure 10.18). Furthermore, high calcium levels in the soil
solution may reduce potassium uptake by the plant. Finally, potassium defi-
ciency has been noted in soils with excess calcium carbonate. Potassium fixa-
tion as well as cation ratios may be responsible for these adverse effects.
10.22 Intensity and Quantity Factors

As was the case for phosphorus, there is need to identify means by which
the power of soils to supply potassium to plant roots can be described and
measured. There are marked differences between the compounds in which
these two elements are found in soils and in the rates at which they are made
available to plants. But the concept of intensity and quantity discussed in
Section 10.14 in relation to phosphorus is also useful in describing and measur-
ing potassium-supplying power.
The intensity factor is a measure of the potassium that is immediately
available to the root-the potassium in the soil solution. Since the absorption
of the potassium ion by plant roots is affected by the activity in the soil solution

18 18
•
16 16
14 14
-;:-
Oii ~.
-"" 12
-. 12
.,
Q.
'0
E Cation exchange capacity .,
<II
~ '0
.§.
.£
..
u
Q.
10 10 c
.2
!;
u
OJ '0
<II
to
C
8 .~
"'
.s:: 8
u
)( .S
c" E
~
.2 ' 0;;
:0 6 6 <II
u 0"'
Q..
4 Soil solution potassium

4
®
2 2
®
0 0
4.0 5.0 6.0 7.0 8.0
pH
FIGURE 10.18 The influence of increased pH resulting from lime additions on the
pH-dependent cation exchange capacity of a soil and the level of potassium in the
soil solution. As the cation exchange capacity increases. some of the soil solution
potassium is attracted to the adsorbing colloids. [Data from Magdoff and Bartlett (1980).]
of other cations and particularly of calcium and magnesium. some authorities

prefer to use the ratio
rather than the K+ concentration, to indicate the intensity factor.

The quantity factor is a measure of the capacity of the soil to maintain
the level of potassium in the soil solution over the period of time the crop is
being produced. This capacity is due mainly to the exchangeable potassium.
although some nonexchangeable forms release sufficient potassium during a

growing season to provide a notabl e portion of the crop needs. The
main point
to remember. however. is that the quantity factor design ates the
potass ium
sources capabl e of helping to replenish the soil solution (intensity)
level of
potassium.
The concept of the buffering capaci ty of the soil. which indica tes
how
the potassium level in the soil solution (intens ity) varies with the
amoun t of
labile forms of this element (quant ity). is useful in explaining differe
nces in
potassium supplying power of soils. The buffering capaci ty (BK+) is
the ratio
of changes in the quantity factor (~Q) to changes in the intensity factor
(~l).
This ratio is high for well-buffered soils and is low for those that
are poorly
l:iu eren and are poor suppliers of potass ium during a growth cycle.
Clay-
textured soils are well buffered. wherea s that those are sandy are
apt to be
poorly buffered.
10.23 Practical Implications in Respect to Pota ssium

Frequency of Application. One very important suggestion that is eviden
t from
the facts thus far considere is that frequent light applications of
potass ium
are usually superior to heavie r and less frequent ones. Such a conclu
sion is
reason able when considering the luxury consumption by crops. the
ease with
which this element is lost by leaching. and the fact that excess potass
ium is
subject to fixation. Although the latter phenomenon has definite conser
ving
features. these are in most cases entirely outweighed by the disadv
antage s
of leaching and luxury consumption.
Potassium· Supplying Power of Soils. A second very import ant sugges

tion is
that full advant age should be taken of the potash-supplying power
of soils.
The idea that each pound of potassium removed by plants or through
leaching
must be returne d in fertilizers may not always be correct. In some
soils the
large quantities of moderately availab le forms already presen t can be
utilized.
Where slowly available forms are not found in significant quantities.
however.
supplementary additions are necessary. Moreover. the importance
of lime in
reducing leaching losses of potassium should not be overlooked as
a means
of effectively utilizing the power of soils to furnish this element.
Potassium Losses and Gains. The problem of maintaining soil potass

ium is
outlined diagrammatically in Figure 10.19. Crop removal of potash
genera lly
exceeds that of the other essenti al elements. with the possible except
ion of

FIGURE 10.19 Gains and losses of available Crop residues Commercial Slowly available
soil potassium under average field conditions. Manures fertilizers potassium minerals "- ,
The approximate magnitude of the changes is \
represented by the width of the arrows. For any \
specific case the actual amounts of potassium \
\
added or lost undoubtedly may vary
considerably from the above representation. As Available soil I
potassium I
was the case with nitrogen and phosphorus, I
commercial fertilizers are important in meeting /
crop demands. I
/
,/
/
Crop Leaching Erosion Fixation - ...-
removal losses losses
nitrogen. Annual losses from plant removal as great as 100 kg/ha of potassium
are not uncommon, particularly if the crop is a legume and is cut several
times for hay. As might be expected, therefore, the return of crop residues
and manures is very important in maintaining soil potash. For example, 10
Mg of average animal manure supplies about 40 kg of potassium, fully equal
to the amount of nitrogen thus supplied.
The annual losses of available potassium by leaching and erosion greatly
exceed those of nitrogen and phosphorus. They are generally not as great,
however, as the corresponding losses of available calcium and magnesium.
The available potassium depletion by erosion assumes great importance consid-
ering that total potassium removal in this manner generally exceeds that of
any other major nutrient element. The loss of potential sources of available
potassium (soil minerals) cannot but eventually be serious.
Increasing Use of Potash Fertilizers. In the past, potash in fertilizers was

added to supplement that returned in crop residues and that obtained from
the slowly available forms of potassium carried by soil minerals. Fertilizer
potash is now depended upon to supply much of the potassium needed for
crop production. This is essentially true in cash-crop areas and in regions
where sandy soils are prominent. Even in some heavier soils, the release of
potassium from mineral form is much too slow to support maximum plant
yields. Consequently, increased usage of commercial potash must be expected
if yields are to be increased or even maintained.
REFERENCES
Acquaye, D. K. 1963. "Some significance of soil organic phosphorus mineraliza-
tion in the phosphorus nutrition of cocoa in Ghana," Plant and Soil, 19:65-
80.
References 361
AUoe. O. J.• and E. Truog. 1945. "Exchangeable and acid soluble potassium
as regards availability and reciprocal relationships." Soil Sci. Soc. Amer.
Proc., 10:81-86.
Black, C. A. 1971. Behavior of Soil and Fertilizer Phosphorus in Relation to
Water Pollution, Jour. Paper J6373, Iowa Agr. and Home Econ. Exp. Sta.
Brady. N. C. 1974. The Nature and Properties of Soils, 8th ed. (New York:
Macmillan).
Douglas. J. R. 1982. "U.S. fertilizer situation-1990," A paper at The Fertilizer
Institute Seventh World Fertilizer Conference, Sept. 12-14, 1982, San Fran-
cisco. CA.
EI-Baruni, B., and S. R. Olsen. 1979. "Effect of manure on solubility of phospho-
rus in calcareous soils," Soil Sci., 112:219-225.
Evans, C. E., and O. J. Attoe. 1948. "Potassium supplying power of virgin and
cropped soils," Soil Sci., 66:323-34.
Fox, R. L. 1981. "External phosphorus requirements of crops," in Chemistry
in the Soil Environment, ASA Special Publication No. 40 (Madison. WI:
Amer. Soc. Agron. and Soil Sci. Soc. Amer.), pp. 223-239.
Gholston, L. E., and C. D. Hoover. 1948. "The release of exchangeable and
nonexchangeable potassium from several Mississippi and Alabama soils
upon continuous cropping." Soil Sci. Soc. Amer. Proc., 13:116-21.
Grewal, J. S., and J. S. Kanwar. 1976. Potassium and Ammonium Fixation in
Indian Soils (Review), (New Delhi, India: Indian Council for Agricultural
Research).
ISMA. 1977. "The importance of phosphorus in agriculture," 1977 issue of Phos-
phorus in Agriculture (ISMA Ltd., World Phosphate Industry Association,
Paris, France).
Larsen, S. 1967. "Soil phosphorus," Adv. in Agron., 19:151-210.
Lindsay, W. L., and H. F. Stephenson. 1959. "Nature of the reactions of monocal-
cium phosphate monohydrate in soils: I. The solution that reacts with
the soil; and II. Dissolution and precipitation reactions involving Fe, Ai.
Mn, and Ca." Soil Sci. Soc. Amer. Proc., 23:12-22.
Magdoff, F. R., and R. J. Bartlett. 1980. "Effect of liming acid soils on potassium
availability." Soil Sci., 129:12-14.
McLean, E. O. 1978. "Influence of clay content and clay composition on potas-
sium availability," in G. S. Sekhon (Ed.). Potassium in Soils and Crops
(New Delhi, India: Potash Research Institute of India), pp. 1-19.
Mengel, K, and E. A. Kirkby. 1980. "Potassium in Crop Production," Adv. in
Agron., 33:59-111.
Olsen, S. R., R. A. Bowman, and F. S. Watanabe. 1977. "Behavior of phosphorus
in the soil and interactions with other nutrients," Phosphorus in Agricul-
ture, 70:31-46.
Sekhon. G. S. (ed.). 1978. Potassium in Soiis and Crops (New Delhi, India:
Potash Research Institute of India).
Toth, S. J., and F. E. Bear. 1947. "Phosphorus-adsorbing capacities of some
New Jersey soils," Soil Sci., 64:199-211.

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Of the various essential elements. nitrogen probably has been subjected to

9.1 Influence of Nitrogen on Plant Development

Oversupply. When higher applications of nitrogen than necessary are made,

284 9 Nitrogen and Sulfur Economy of Soils

9.2 Forms of Soil Nitrogen

9.3 The Nitrogen eyelet

9.3 The Nitrogen Cycle 285

286 9 Nitrogen and Sulfur Economy of Soils

9.4 Immo bilization and Mine raliza tion

9.4 Immobilization and Mineralization 287

Mineralization seems to proceed to the best advantage in well-drained

9.5 Utilization of Ammonium Compounds

9.6 Ammonia Fixation

Fixation by Clay Minerals. Several clay minerals with a 2:1-type structure

NH. + ;:= NIl.+ ;:= NH. +

Ammonium fixation by clay minerals is generally greater in subsoils than

Fixation by Organic Matter. Anhydrous ammonia or other fertilizers that con-

9.8 Ammonia Fixation 289

Soil depth Fixed Nil. + nitrogen

Maracas Mica, kaolinite, geothlte (}-10 28.5

• From Dalal (1977).

290 9 Nitrogen and Sulfur Economy of Soils

Organisms Concerned. Although some heterotrophic bacteria. fungi. and acti-

Rate of Nitrification. Under ideal temperature. soil. and moisture conditions.

9.8 Soil Conditions Affecting Nitrification

Aeration. Since nitrification is a process of oxidation, any practice that in-

9.8 SoU Conditions AlJecting Nitrification 291

Temperature. The temperature most favorable for the process of nitrification

Moisture. Nitrification is markedly influenced by soil water content. the pro-

Carbon/Nitrogen Ratio. The significance of the carbon/nitrogen ratio has been

292 9 Nitrogen and Sulfur Economy of sons

Pesticides. Nitrifying organisms are quite sensitive to some pesticides. If

9.9 Fate of Nitrate Nitrogen

9.9 Fate of Nitrate Nitrogen 293

Reduction by Organisms. The reduction of nitrate nitrogen to gaseous com-

-2 [OJ -2 [OJ - [OJ -[OJ

Each step in the reaction is triggered by a specific reductase enzyme.

294 9 Nitrogen and Sulfur Economy of Soils

2 HNOz + CO(NHz)2 - CO 2 + 3 H20 + 2 Nz T

9.10 Denitrification 295

296 9 Nitrogen and Sulfur Economy of Soils

O,g,mk "'''''''" • ~';t;"":::.)

FIGURE 9.5 Nitrification-denitrification reaction and kinetics of the related processes

9.10 Denitrification 297

TABLE 9.2 Examples of Inhibitors of Nitrification-

Common name or symbol Chemical name

Dd. DNDN. Dicyan Dicyandiamide

• From Hauck (1980).

Response to nitrapyrin is variable and depends to a considerable extent

Sulfur-Coated Urea. Another means of reducing gaseous loss of nitrogen is

298 9 Nitrogen and Sulfur Economy of Soils

Sanda Poor Fair Fair

• Chance of increase at any location any year, Poor =

the availability of nitrates for the denitrification process. Unfortunately, how-

9.12 Ammonia Volatilization

9.12 Ammonia Volatilization 299

The Mechanism. Although biological nitrogen fixation is accomplished by a

TABLE 9.4 Biological Nitrogen Fixation from Different Sources-

Nitrogen fixed per year

o ~~ ~ ~ __________________ ~