NITROGEN IN SOILS/Cycle 13

NITROGEN IN SOILS

Contents
Cycle
Nitrates
Nitrification
Plant Uptake
Symbiotic Fixation

Cycle soil is driven by these transformations between

M S Coyne and W W Frye, University of Kentucky,
Lexington, KY, USA
ß 2005, Elsevier Ltd. All Rights Reserved.
Introduction
Nitrogen (N) is the element most often limiting plant
nutrition in terrestrial ecosystems. The greatest source
of available N is atmospheric dinitrogen (N2), which
is relatively inert and can only be used by symbiotic
and free-living prokaryotic bacteria with the capacity
for N2 fixation (Table 1). For other plants and soil
organisms, the slow release of N from rocks and
minerals and cycling between organic and inorganic
forms in soil is crucial to life. Unfortunately, some
aspects of N cycling can be problematic. Nitrogen
can be readily lost from terrestrial soils, leading
to reduced fertility and surface- or groundwater
contamination, and several transformations give rise
to intermediate or final products that can have
negative environmental consequences.
oxidized and reduced states and between organic
and inorganic forms (Figure 1).
The principal soluble inorganic N forms in soil
are NO

þ
3 , NO2 , and NH4 . The inorganic gase-
ous N forms in soil are N2, N2O, NO, and NH3.
Organic N takes many forms, such as amino acids
(e.g., glycine, glutamine), amino sugars (e.g., glucosa-
mine, galactosamine), nucleosides (e.g., adenine,
guanine), peptides, phospholipids (e.g., phospha-
tidylethanolamine, phosphatidylserine), vitamins
(e.g., niacin), and other compounds such as creatine,
cyanide, allantoin, various alkyl amines, and urea.
Unidentifiable forms of N are typically polymerized
with soil organic matter fractions such as humic and
fulvic acids.
N-Cycling Pathways
The major organic and inorganic N transformations
that occur in soil can be grouped into five pathways:
mineralization (ammonification), assimilation (im-
mobilization), nitrification, nitrate reduction, and
N2 fixation.

Properties and Forms of Nitrogen

in Soil
There are two overriding chemical properties of the Table 1 Global sources of available N
N atom worth noting. First, the dinitrogen molecule, Source N content (1016 kg)a Total (%)
N2, is very stable. Once formed and lost from the soil
environment, N2 is relatively inert and requires con- Atmosphere 386.000 87.0000
Oceans and lakes
siderable energy (946 kJ mol
1) to break the triple
Dissolved N2 2.190 0.5000
bond between N molecules and reintroduce N to bio- Soluble inorganic N 0.110 0.0200
logical systems. The second significant feature of N, Sediments 35.000–55.000 12.0000
owing to its atomic structure and electron configur- Sea bottom organic N 0.054 0.0100
ation, is its ability to undergo changes in oxidation Terrestrial biosphere 0.028–0.065 0.0100
Terrestrial soils
state from þ5 to
3 depending on its environment.
Organic N 0.022 0.0050
This property is important for soil transformations, Clay-fixed NHþ
4 0.002 0.0005
because N, in its oxidized forms, can be an electron
a
acceptor in anaerobic respiratory metabolism. N, in The data exclude N in the lithosphere such as igneous rocks, sediments,
and coal that do not actively participate in global N cycling.
its reduced forms, can also be an energy source for Source: Stevenson FJ and Cole MA (1999) Cycles of Soil, 2nd edn. New York:
various chemolithotrophic bacteria. The N cycle in John Wiley and Sons, Inc.
14 NITROGEN IN SOILS/Cycle
Figure 1 Oxidation–reduction transformations of nitrogen.
Mineralization (Ammonification)
During mineralization, organic N is hydrolyzed to
release NH3, which is subsequently protonated in
the soil solution to become the cation NHþ 4 (eqn
[1a]). Consequently, mineralization is frequently
referred to as ammonification:
Another example of mineralization that has great
importance in soil is urea hydrolysis by the seemingly
ubiquitous enzyme urease, which is shown in eqn [2].
Urea is one of the dominant organic N forms excreted
by animals, and it is also one of the most popular
forms of solid fertilizer used on a global basis. Urea
hydrolysis in soil is rapid, and the subsequent NH3
formation can cause considerable N loss through
volatilization. One of the immediate effects of urea
hydrolysis is also a rapid increase in the soil pH:
Assimilation (Immobilization)
Assimilation (immobilization) is the incorporation of
inorganic N as NHþ


4 , NO3 , or NO2 into biomass
(eqns [3] and [4]). Immobilization can also refer to
the binding of NHþ 4 to certain clays in soil and to the
interaction of inorganic N with soil organic matter:
Nitrification
Nitrification is the general term that describes
oxidation of reduced inorganic and organic N and
formation of NO


2 or NO3 . It is an aerobic process
that occurs by one of two pathways: autotrophic
nitrification, carried out by chemolithotrophic bac-
teria, and heterotrophic nitrification, carried out by
chemoheterotrophic bacteria and fungi.
Autotrophic nitrification Autotrophic nitrification
is a two-step process that is carried out by chemo-
lithotrophic bacteria, which obtain energy by
oxidizing NH3 to NO
3 (eqn [5]).
The first step in the pathway, which is performed
by NH3-oxidizing bacteria such as Nitrosomonas,
involves the sequential oxidation of NH3 to hydro-
xylamine (NH2OH) and then to NO
2 (eqns [6a]
and [6b]):
The second step in the pathway is performed by
NO
2 oxidizing bacteria typified by bacteria in the
genus Nitrobacter. Nitrite oxidation is generally so
rapid that NO
2 rarely accumulates to any significant
extent in soil:
Autotrophic nitrification is believed to be the dom-
inant type of nitrification occurring in agricultural
soils. Nitrification is an acidifying process and use
of reduced organic and inorganic N for plant nutri-
tion will lower the soil pH with time because of
nitrification.
Heterotrophic nitrification Heterotrophic nitrifica-
tion is the oxidation of organic N and NH3 by various
chemoheterotrophic bacteria and fungi such as
Arthrobacter, Streptomyces, and Aspergillus. Hetero-
trophic nitrification produces NO


2 and NO3 in soils
typically too acid to permit autotrophic nitrification
(eqn [8a]).
 NITROGEN IN SOILS/Cycle 15

aquatic systems, photosynthetic cyanobacteria such

as Anabaena and Nostoc are responsible for N2
Products of heterotrophic nitrification also include fixation.
nitroso-compounds, which have been identified as
potential carcinogens (eqn [8b]):

Nitrogenase is actually an enzyme complex consist-

Nitrate Reduction
In anaerobic or waterlogged environments, denitrifi-
cation and dissimilatory nitrate reduction to ammo-
nium (DNRA) are the two major pathways by which
the NO


2 and NO3 formed by nitrification can be
subsequently reduced. Facultatively anaerobic bac-
teria perform these N transformations, although it
has been suggested that some fungi are also capable
of denitrification.
Denitrification Denitrification is the major reduc-
tive fate of NO
3 in most soil environments. It is a
respiratory process in which nitrogen oxides are used
as terminal electron acceptors in place of O2 and
produces gas as the terminal reduction product (eqn
[9]). Denitrification is a multistep process catalyzed
by distinct enzymes for each step:
ing of dinitrogenase reductase and dinitrogenase,
which are highly conserved, O2-sensitive enzymes
working in tandem to reduce N2. Nitrogenase is
somewhat nonspecific with respect to substrate, so it
will also reduce Hþ to H2, N2O to N2, and C2H2 to
C2H4. The latter reduction is the basis for the acetyl-
ene reduction assay (ARA), which is used to detect
and quantify N2 fixation in different environments.
Fixed (Nonexchangeable) Ammonium
An important part of the inorganic soil N of some
soils is fixed or nonexchangeable NHþ 4 . Ammonium
ions in soil exist in a chemical equilibrium as follows:
NHþ þ þ
4 ðsolutionÞ$ NH4 ðexchangeableÞ $ NH4 ðfixedÞ
Figure 2 shows the crystalline structure of a wea-
thered, micaceous silicate clay mineral, such as
illite, showing the locations of solution, exchange-
able, and fixed NHþ 4 . Much of the fixed NH4
þ

can be slowly available to growing plants and soil

Dissimilatory nitrate reduction to ammonium The

NHþ 4 produced during DNRA is not assimilated but is
excreted into the environment (eqn [10]). The bac-
teria that perform DNRA are distinct from denitri-
fiers. They predominate in environments that are
continuously saturated, anaerobic, and have high
concentrations of available C relative to NO

3:

N2 Fixation
Nitrogen fixation is an energy-demanding process by
which prokaryotic bacteria reduce N2 gas to NH3
either independently or in symbiosis with various
leguminous and nonleguminous plant species (eqn
[11]). The most significant types of terrestrial nitrogen
fixation are the legume/rhizobia symbiosis and
the actinorhizal symbioses, which occur between
woody shrubs and bacteria of the genus Frankia. In
Figure 2 Schematic of micaceous-type soil clay (vermiculite,
hydrous mica) showing wedge-shaped zones and weathered
edges where NH+ 4 can be fixed. Adapted from Dixon JB and
Weed SB (eds) (1989) Minerals in Soil Environments, 2nd edn. Soil
Science Society of America Book Series 1. Madison, WI: Soil
Science Society of America with permission.
16 NITROGEN IN SOILS/Cycle

microorganisms. As plant uptake or biomass immo-
bilization depletes the readily available NHþ 4 , i.e.,
solution NHþ þ
4 and exchangeable NH4 , fixed NH4 is
þ
released by cation replacement, especially with Kþ.
Conversely, when NHþ 4 is added to the soil from any
source, more NHþ 4 is fixed to establish a new equilib-
rium. Therefore, the fixed NHþ 4 sites serve as a
reserve source of N and as a sink for excess NHþ 4.
Regulation and Environmental Control
Nitrogen transformations between organic and inor-
ganic forms in soil depend on the type and availability
of inorganic N and on the relative availability of
inorganic N to mineralizable C.
Cellular and Environmental Regulators of
N Transformations
Microorganisms in soil will preferentially assimilate
NHþ


4 rather than NO3 or NO2 . Even low NH4
þ
concentrations in soil solutions will quickly stop
NO
3 uptake and, soon after, inhibit enzymes associ-
ated with assimilatory NO
3 reduction (Table 2). If
NHþ 4 concentrations in soil solutions exceed
1 mmol l
1, assimilation by glutamate dehydrogenase
will occur in which the first recognizable product is
glutamate. If soil N is limiting, microorganisms will
utilize an enzyme system referred to as GS/GOGAT
(glutamine synthetase/glutamine oxoglutarylamino
transferase) in which the first identifiable form of
organic N is glutamine. Nitrate, if it is assimilated,
will first be reduced to NO
2 by assimilatory NO3




reductase and the NO2 subsequently reduced to
NHþ

4 by assimilatory NO2 reductase. Thereafter,
the pathways are the same as for NHþ 4 assimilation.
Organic N will be mineralized in soil in the absence
of available inorganic soil N, although, as a general
rule, N-containing compounds such as amino acids
are not mineralized only to be subsequently resynthe-
sized. Most N cycling in soil and inorganic N release
is actually driven by the mineralization of soil C for
biomass and energy; inorganic N accumulates in soil
only when the microbial demand for N is met. When
the C/N ratio of decomposing material exceeds ap-
proximately 30, net immobilization of inorganic
N from soil occurs because there is insufficient N in
the mineralizing material to sustain microbial bio-
mass formation. In contrast, when the C/N ratio is
less than 30, the N needs for microbial growth are
met, and inorganic N is released into the soil environ-
ment. The decomposition of organic materials with
very low C/N ratios can therefore cause inorganic
N to accumulate briefly in excess of microbial and
plant needs, with the potentially adverse effects of
volatilization, runoff loss, or plant toxicity in the
case of NHþ 4.
The three environmental factors that regulate nitri-
fication in soil are NHþ 4 availability, aeration, and pH
(Figure 3). As long as the oxidation–reduction poten-
tial (Eh) of soil exceeds approximately 400 mV, NO
3
will remain oxidized and nitrification of NHþ 4 will
proceed. In contrast to most other N transformation
processes, autotrophic nitrification is extremely pH-
sensitive. Below pH 5.5, NHþ 4 oxidation will not
occur, and above pH 8 NO
2 oxidation slows, because
NH3 inhibits NO
2 -oxidizing bacteria. Ammonifica-
tion and urease activity can rapidly increase the NH3
concentration in soil sufficiently to prevent NO
2 oxi-
dation and thereby cause brief NO
2 accumulation.
Plant toxicity can result.
In grassland and prairie environments, autotrophic
nitrification is often minimal. Although it has been
suggested that this is due to allelopathic effects of
the native vegetation, the most likely explanation is

Table 2 Inhibition of NO
þ

3 assimilation by NH4

NO3
concentration Response

(mg NO3
-N ml
1) N source Inhibition (%) time (min)

2 NHþ4 55 1
Arginine 51 6
Asparagine 50 1
Glutamine 48 4
Glutamate 22 nd
Aspartate 21 nd
Alanine 8 nd
Glycine 1 nd
10 NHþ4 79 5
Glutamine 72 3

nd, not detectable.

Source: Rice CW and Tiedje JM (1989) Regulation of nitrate assimilation by
ammonium in soils and in isolated soil microorganisms. Soil Biology and Figure 3 Regulators of nitrification in the soil environment.
Biochemistry 21: 597–602. CEC, cation exchange capacity.

that intense competition from plant roots and he-
terotrophic microorganisms deprives nitrifiers of the
NHþ 4 that they require for growth.
Nitrification slows and ceases as soils become in-
creasingly saturated. The dominant fate of NO
3 in
most waterlogged soil environments is denitrifica-
tion. Oxygen concentration is the overwhelming en-
vironmental factor controlling denitrification and
DNRA (Figure 4). Limited C and NO
3 availability
will also slow denitrification and affect whether
incompletely reduced intermediates such as NO and
N2O accumulate.
Environmental control over whether denitrifica-
tion or DNRA predominates in an environment
appears to be governed by the extent and duration
of anoxia and by the relative proportions of soluble
C and NO
3 (Figure 5). Denitrifiers are more competi-
tive when C is limiting because they obtain more
Figure 4 Regulators of NO
3 reduction in the soil environment.
AEC, anion exchange capacity.
Figure 5 Environmental control of the partitioning between
denitrification and dissimilatory nitrate reduction to ammonium
(DNRA). Adapted from Tiedje JM, Sexstone AJ, Myrold DD, and
Robinson AJ (1982) Denitrification: ecological niches, competi-
tion, and survival. Antonie van Leeuwenhoek 48: 569–583.
NITROGEN IN SOILS/Cycle 17
energy through anaerobic respiration with NO
3
than do NHþ 4 dissimilators (1121 versus 600 kJ
mol
1 of NO
3 reduced).
Nitrogen fixation is an energy-demanding process.
Consequently, when N is available in the form of
inorganic N or readily mineralizable organic N, the
synthesis and activity of nitrogenase are suppressed.
High soil N concentrations will also suppress the
establishment of symbiotic N2-fixing relationships
between bacteria and plants.
Chemical Regulators of N Transformations
Chemicals have been developed that can effectively
regulate (inhibit) two important N transformations
on an agricultural field scale – nitrification and urea
hydrolysis. A nitrification inhibitor slows the rate of
autotrophic nitrification by selectively suppressing
Nitrosomonas bacteria in the soil (eqn [5]). A urease
inhibitor functions by interfering with the enzymatic
activity of urease in catalyzing the hydrolysis of urea
(eqn [2]). The use of these chemicals will be discussed
later as part of management practices to decrease
N losses.
Routes of N Loss From the Environment
The N transformations in soil inevitably result in
intermediate or final products that can be lost from
the soil environment through gaseous diffusion,
leaching, or surface erosion (Figure 6). The route of
N loss greatly depends on the type of transformation –
whether oxidative or reductive.
Reductive Losses
The major reductive losses of N occur during denitri-
fication, which produces N oxides such as NO and
N2O as intermediates and N2 as a final product. All
three compounds are gases that can be lost to the
atmosphere. Nitrate reduction to NHþ 4 seemingly
preserves N from loss; however, the NHþ 4 formed
can still be leached in soils with low cation exchange
capacities or lost through erosion.
Oxidative Losses
Autotrophic nitrification frequently results in the
production of NO and N2O as gaseous intermediates.
The major concern with nitrification is the
production of NO
3 , which is readily leached from
soil environments.
Volatilization
Ammonium exists in chemical equilibrium with NH3.
The pK for this equilibrium is approximately pH 9.5.
Consequently, when the soil pH is sufficiently high, or
18 NITROGEN IN SOILS/Cycle

Figure 6 Paths of nitrogen transformation and loss from soil. Numbered pathways correspond to the chemical equations in the text.

Table 3 Some patented nitrification inhibitors

Chemical Common name Developer Inhibition by day 14 (%)

2-Chloro-6-(trichloromethyl)pyridine N-serve Dow Chemical 82

4-Amino-1,2,4-6-triazole-HCl ATC Ishihada Industries 78
2,4-Diamino-6-trichloromethyltriazine CL-1580 American Cyanamid 65
Dicyandiamide DCD Showa Denko 53
Thiourea TU Nitto Ryuso 41
1-Mercapto-1,2,4-triazole MT Nippon 32
2-Amino-4-chloro-6-methylpyrimidine AM Mitsui Toatsu 31

Adapted from Paul EA and Clark FE (1989) Soil Microbiology and Biochemistry. San Diego, CA: Academic Press with permission.

if NHþ4 production is sufficiently rapid, aqueous NH3

will be volatilized from soil and lost to the atmos-
phere as a gas. Animal manures, which contain read-
ily mineralizable forms of organic N such as urea, can
produce considerable amounts of volatile NH3 due to
this process.
Interaction of N with Soil Organic Matter
A significant fate of inorganic N is its interaction with
soil organic matter. Although this can retard N loss
from the environment, it also temporarily renders
part of the inorganic N unavailable. Studies in Cali-
fornia and Iowa have demonstrated that much of the
inorganic NO
þ
3 and NH4 added to soil can almost
immediately become immobilized. Nitrification-
mediated immobilization involves the reaction of
NO
2 , formed during the first step of nitrification,
with soil organic matter at acidic and neutral pH to
form nitrosophenols. Nitrite can also react with
amino acids and other forms of reduced organic N to
liberate gases as illustrated in eqns [12] and [13]:
Management Practices to Decrease N Losses
Figure 6 shows the transformation pathways that
potentially result in losses from the N cycle. Some of
these losses, including soil erosion, NO
3 leaching,
denitrification, and NH3 volatilization, can be man-
aged to varying extents. Inhibiting nitrification and
urease activity affects all of these pathways except
erosion.
Nitrification inhibitors Several chemicals have been
shown to inhibit nitrification (Table 3), but few have
been proven agronomically and economically effect-
ive. The first nitrification inhibitor to be approved by
the US Environmental Protection Agency was nitra-
pyrin, manufactured by Dow Chemical Company
 NITROGEN IN SOILS/Cycle 19

and marketed as N-Serve. Nitrapyrin is 2-chloro-6- Table 4 Corn yield response to urease inhibitors with fertil-
(trichloromethyl) pyridine. It may be used with any izers surface applied for no-tillage corn
NHþ 4 -N fertilizer, including anhydrous ammonia, Grain yields (Mg ha
1)
urea, urea–ammonium nitrate solutions (UAN), am-
Fertilizer a Pennsylvania b Kentucky c
monium nitrate, ammonium sulfate, and animal
manures. UAN 6.96 5.14
Nitrapyrin has a relatively high vapor pressure (2.8 UAN þ ATS 7.03 NS –
UAN þ NBPT 7.40 5.52
 10
3 mmHg at 23 C). Because of its tendency to
Urea 6.65 5.27
volatilize, the manufacturer initially recommended Urea þ NBPT 7.53 6.15
incorporation into soil immediately after application. Ammonium nitrate 7.59 5.96
Research in Kentucky showed that nitrapyrin was a
UAN, urea ammonium nitrate solution; ATS, ammonium thiosulfate;
effective when sprayed directly on to N fertilizer NBPT, N-(n-butyl) thiophosphoric triamide.
particles, which were then surface-applied for no- b
From Fox and Piekielek (1993).
c
tillage corn. The researchers believed that the imme- Unpublished data, Department of Agronomy, University of Kentucky.
NS, not significantly different (P
0.10) by LSD.
diate proximity of nitrapyrin and NHþ 4 ions together
at the sites of nitrification facilitated its effectiveness,
even when surface-applied.
Dicyandiamide (DCD), also known as cyanoqua-
nidine, is a water-soluble, organic amide that is both a
slow-release N source and a nitrification inhibitor.
The composition of DCD is C2N4H4, and it contains
at least 65% N. It is a fine-grained, nonhygroscopic,
crystalline powder, which is easily incorporated into
solid, solution, or suspension fertilizers.
Widespread research on nitrapyrin and DCD
shows generally that both are very effective in sup-
pressing nitrification in soil for several weeks after
application. The ratio of NHþ

4 to NO3 is usually


much higher in soils, and NO3 is lower in drainage
water from soils following application of ammonical
fertilizers treated with nitrapyrin or DCD than
the same applications without a nitrification inhibi-
tor. A crop yield response to a nitrification inhibitor,
however, occurs only if N was lost by leaching or
denitrification and then only if those losses resulted
in N deficiency sufficient to reduce yields without the
nitrification inhibitor. Rarely are yield increases ob-
served if nitrification inhibitors are used with much
higher than optimum application rates of N. The en-
vironmental benefits of decreasing NO
3 leaching
with a nitrification inhibitor would none the less be
present and even more important where an excess of
N was applied.
Urease inhibitors As in the case of nitrification
inhibitors, several chemicals inhibit urease activity.
Because mechanical incorporation is usually not prac-
tical, a urease inhibitor must suppress hydrolysis of
broadcast-applied urea to the surfaces of soil and
plant residues for no-tillage agriculture, or growing
plants in pastures, forage fields, or lawns, and the
effect must last long enough to allow rainfall to
leach the urea molecules into the soil, where hydroly-
sis can occur with little risk of NH3 volatilization loss
from most soils.
Significantly different by LSD: P  0.10, P  0.01, respectively.
In many research studies (examples shown in
Table 4), one urease inhibitor has been shown to be
particularly efficacious for urea fertilizer manage-
ment. Allied Chemical Corporation patented N-
(n-butyl)thiophosphoric triamide (NBPT) as a urease
inhibitor in 1985. Today, NBPT is marketed by
Agrotain International as a technology entity that
includes a practical means of treating solid urea or
UAN solution with NBPT, or NBPT and DCD, at a
fertilizer-blending facility and delivering the product
in the field as a fertilizer application. The combination
of NBPT and DCD provides urease and nitrification
inhibition for a urea application.
Environmental and Health Consequences
of N Cycling
The principal environmental and health concerns as-
sociated with N cycling in soil are the potential for
trace gas production and its effect on global warming
and ozone depletion, the potential for nutrient loss,
and the movement of N to environments where it can
cause eutrophication and potential health problems.
Global Warming and Ozone Destruction
Nitrous oxide and nitric oxide are trace gases formed
during nitrification and denitrification transform-
ations of N in soil. Molecule for molecule, N2O is
150 times more effective at adsorbing thermal radi-
ation than is CO2, the major greenhouse gas. Nitric
oxide plays a well-known role in the destruction of
stratospheric ozone as illustrated in the following
reactions:
O3 þ hv ! O2 þ O ½14
N2 O þ O ! 2NO ½15
20 NITROGEN IN SOILS/Cycle

NO þ O3 ! NO2 þ O2 ½16 Mississippi River and its tributaries. Due to nutrient

leaching from agricultural watersheds, a hypoxic
NO2 þ O ! NO þ O2 ½17 zone some 7000 square miles in size (approximately
the same area as the state of New Jersey), which has
Nutrient Losses
significantly affected the shrimp and shellfish indus-
tries, has developed in the Gulf of Mexico off the
Denitrification and NO
3 leaching have been associ- Louisiana coast.
ated with the loss of up to 70% of the inorganic N in
some fertilized fields. Ammonia volatilization occur-
ring during hydrolysis of urea (eqn [2]) can result in Conclusion
losses of 10–50% of the N from surface-applied urea
The N cycle in soil is dynamic and inherently leaky.
fertilizers. Ammonia volatilization due to urease
Off-site losses of N gases, soluble ions, and organic
activity is given as one explanation for the loss of
compounds are virtually impossible to eliminate
3–50% of the N in unincorporated manures such as
completely. Nevertheless, there are several manage-
poultry litter applied to neutral soils. Ammonia in
ment practices for erosion control and fertilizer use
high enough concentrations is a toxic gas, and its
that can minimize N losses from soil, and the cycle
production in confined animal feeding operations
itself can be used to preserve environmental quality.
(CAFOs) is a major concern. Unfortunately, venting
For example, biological N2-fixation rather than com-
such gases into the atmosphere is problematic for two
mercial fertilization will generally retain more soil
reasons. First, the volatile N gases are odoriferous
N. Nitrates and nitrites in groundwater have been
and generate nuisance complaints. Second, the vola-
remediated through denitrification on increasingly
tile gases eventually return to soil or water as wet and
larger scales to preserve groundwater quality and
dry deposition and can contribute to eutrophication
public health.
in pristine environments.
Groundwater Quality
List of Technical Nomenclature
Groundwater is the source of drinking water for more
Anoxia Conditions in which O2 is absent. Syn-
than half of the USA, and in rural areas it represents
onymous with ‘anaerobic’
more than 95% of the water used for domestic pur-
poses. Nitrate-N concentrations in streams and Autotrophy Growth using inorganic elements as
groundwater are typically less than 2 mg l
1 but C and energy sources
have been steadily increasing in the USA and Europe. Biomass Living organisms in soil, whether plants,
In the USA, for example, well-drained soils receiving animals, or microorganisms
high N inputs have median NO
3 -N concentrations
approaching 5 mg l
1 and up to 26% of sample wells Eutrophic Excessive growth typically associated
have levels exceeding 10 mg NO

1 with aquatic systems in which one or
3 -N l , which is the
more limiting nutrients such as N or P
US Environmental Protection Agency (USEPA) and
is provided
Public Health Service drinking water standard. Many
drinking water systems in Europe currently exceed Heterotrophy Growth using organic C as the source of
the EC limit of 11.3 mg l
1. C for biomass production and for energy
The consequences of chronic consumption of Hydrolysis Addition of water to chemical bonds
NO
3 -contaminated drinking water and vegetation during chemical reactions
can be severe and include methemoglobinemia
(blue-baby syndrome) and increased potential for Inhibition Suppression or slowing of a process for
an indefinite time, usually a few weeks
stomach cancer due to nitrosamine formation.
The consequences of nitrification and subsequent
See also: Enzymes in Soils; Greenhouse Gas Emis-
NO
3 leaching also have severe ecological conse-
sions; Microbial Processes: Environmental Factors;
quences. The inability of growing plants to capture Nutrient Management
completely the N applied in fertilizer, and natural
mineralization and nitrification in undisturbed soils
opened to agriculture, grazing, and irrigation, has Further Reading
caused N pollution problems from the Chesapeake Dixon JB and Weed SB (eds) (1989) Minerals in Soil
Bay in the eastern USA to the Baltic. The Gulf of Environments, 2nd edn. Soil Science Society of America
Mexico, for example, receives drainage from ap- Book Series 1. Madison, WI: Soil Science Society of
proximately 41% of the continental USA via the America.

Fenchel T, King GM, and Blackburn TH (1998) Bacterial
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Follett RF, Keeney DR, and Cruse RM (1991) Managing
Nitrogen for Groundwater Quality and Farm Profitabil-
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Fox RH and Piekielek WP (1993) Management and urease
inhibitor effects on nitrogen use efficiency in no-till corn.
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Paul EA and Clark FE (1989) Soil Microbiology and Bio-
chemistry. San Diego, CA: Academic Press.
Pearce RC, Zhan Y, and Coyne MS (1998) Nitrogen trans-
formations in the tobacco float system. Tobacco Science
42: 82–88.
Rice CW and Tiedje JM (1989) Regulation of nitrate as-
similation by ammonium in soils and in isolated soil
microorganisms. Soil Biology and Biochemistry 21:
597–602.
Schlesinger WH (1997) Biogeochemistry: an Analysis of
Global Change, 2nd edn. San Diego, CA: Academic
Press.
Spalding RF and Exner ME (1993) Occurrence of nitrate in
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Nitrates
D S Powlson and T M Addiscott, Rothamsted
Research, Harpenden, UK
ß 2005, Elsevier Ltd. All Rights Reserved.
Under aerobic conditions nitrate (NO
3 ) is the final
form of nitrogen produced in soil following the de-
composition of soil organic matter or any added plant
or animal material. It is the main chemical form in
which nitrogen is taken up by plants, though most
NITROGEN IN SOILS/Nitrates 21
plants can also absorb N in the ammonium form
(NHþ 4 ). Figure 1 shows the central position of soil
nitrate within the nitrogen cycle. Nitrate is a natural
product that is almost always present in soil. In nat-
ural or seminatural ecosystems nitrogen is usually
cycled very efficiently between soil microbes, soil
solution, and plants so the concentration of nitrate
in soil at any time is normally low and losses are
small. By contrast, in order to grow large yields of
agricultural crops, nitrogen is required in large
quantities. For example, winter wheat growing
under UK conditions would typically take up about
200 kg N ha
1 and most agricultural crops, other than
those grown under subsistence farming conditions,
take up between 100 and 200 kg N ha
1. Various
practices are adopted in order to provide sufficient
N and the use of inorganic fertilizers is particularly
important, with almost 80 million tonnes of N being
used annually worldwide (Table 1). Inorganic fertil-
izers either contain nitrate or forms of N such as
ammonium or urea that are rapidly converted to ni-
trate by soil microorganisms. Alternatively N may be
supplied by adding animal manure or by incorporat-
ing residues of plants rich in nitrogen, such as N-fixing
legumes, which may have been grown as the previous
crop, as a green manure or as part of a pasture which is
then plowed up. In all cases, except in anaerobic con-
ditions such as flooded rice, much of the N from these
organic sources will be converted to nitrate before
being absorbed by the crop. It is highly desirable to
utilize N from organic materials but it is mistaken to
assume that losses of nitrate are necessarily less than
with inorganic fertilizers as the production of nitrate
from organic sources is determined by the activity of
soil microorganisms and not by crop demand – some
nitrate is produced at times when crop uptake is small
and the risk of nitrate loss is large.
The nitrate ion is extremely soluble in water and
can easily be washed out of soil to natural waters.
There are two main pathways by which nitrate ions
dissolved in soil water are lost through the movement
of water: (1) leaching – the vertical movement of
water and its solutes through the soil profile to either
groundwater or field drains; and (2) surface runoff –
the horizontal movement of water and solutes over
the soil surface until it reaches a river or lake. Surface
runoff occurs where the soil is either compacted or is
naturally poorly draining, e.g., due to high clay con-
tent. A variation on surface runoff is sometimes
termed subsurface flow, in which water infiltrates
the soil to some extent but then moves horizontally
due to impeded drainage, for example due to compac-
tion at the base of the plow layer in cultivated soil or
because of a change in soil physical properties with
depth.