56 P.F. Pratt and W.A.

Jury

ofN from the soil system are by these three processes. For protection of ground-
water from NO;- accumulations, the removal in harvested products and/or deni-
trification must be maximized. Because denitrification is an economic loss, the
ideal management of croplands must maximize removal in harvested products.
Tanji et al. (1977, 1979) expanded this conceptual model, originally presented
by Fried et al. (1976) to include transient changes in N within the soil system and
fluxes of water through the soil profile (the root zone). When tested with 2 years
of data from com field trials at Davis, California, computed results compared fa-
vorably with (1) N in the grain plus stover, (2) the residual inorganic soil N after
harvest, and (3) the NO;- concentration in the drainage water below the root
zone.
Assuming losses by erosion and by volatilization of NH3 are negligible, the
mineral N added to or produced in soils can be assimilated by absorption by plant
roots or by microorganisms, converted to N 20 and/or N2 by denitrification or
leached from the root zone in percolating water. The distribution of mineral N
among these three processes depends on the many variables that control them.
Absorption by plants is dependent on the species and variety and on the many
factors that influence growth. Denitrification is increased by decrease in O 2 sup-
ply, increase in available C in the soil, and by increase in temperature within the
temperature range normally found in soils. Denitrification is usually complete in
flooded soils. In well-aerated, well-drained sands, denitrification is very slow. But
denitrification does occur in poorly aerated microvolumes of soils that are well
aerated from a macroscopic point of view.
As a first approximation, NO;- in the soil system, including the unsaturated
zone beneath the soil root zone, moves with and at the same rates as the move-
ment of the percolating water. However, the relative rate of flux ofNO;- with re-
spect to that of water is dependent on the chemical properties of the soil material.
The relative NO;- flux in positively charged soil materials that adsorb NO;- is less
than unity, whereas in negatively charged soil materials that repel NO;-, it is
greater than unity. In soils with little negative or positive charges, the relative flux
is near unity.
A number of investigators have found that acid kaolinitic and amorphous
soils adsorb NO;- and that this adsorption is greatest in volcanic ash derived soils
having largely allophanic minerals (Rich and Thomas 1960, Thomas 1960, Singh
and Kanehiro 1969, Kinjo and Pratt 1971, Schalscha et al. 1974). Kinjo and Pratt
(1971) and Leon and Pratt (1974) found that 3 or 4 pore volumes of effiuent were
required to move peak concentrations ofNO;- to the bottom of columns ofallo-
phanic subsoil materials and that about 6 or 7 pore volumes were required to re-
move essentially all of the NO;-.
On the other extreme, the flux ofNO;- in soils that contain dominantly smec-
tite clays (montmorillonites and micaceous minerals) is faster than that for water
because of anion exclusion from a fraction of the soil water (Berg and Thomas
1959, Dyer 1965, Thomas and Swaboda 1970, Smith 1972, Bresler 1973a, Bresler
and Laufer 1974, Appelt et al. 1975, Tullock et al. 1975). Tullock et al. (1975) cor-
related the relative rate of flux of Cl- and water through laboratory columns with
the cation-exchange capacity (CEC) of soils. From all comparative studies, the
movement of Cl- and NO;- behave identically in such studies so that data for Cl-
 Pollution of the Unsaturated Zone with Nitrate 57

can be used to predict the behavior of NO;. Relative flux for NO; and/or CI-
in such column studies range from 1.0 to 2.0 for soils containing smectite clays,
indicating that the effects of exclusion volume can be demonstrated in laboratory
columns. However, the practical effects of both negative adsorption (exclusion
volume) and positve adsorption on the movement of NO; in field situations have
not been demonstrated.

4.5 Movement

All dissolved chemicals, including the species ofN, move through the soil by
convection and diffusion. The former process refers to mass flow of solute with
moving water and the latter process to movement within fluid by molecular col-
lisions. Under most conditions, diffusion is small compared with convection. In
addition, there is a spreading of solute due to multidimensional convection paths
in soil, which is known as hydrodynamic dispersion. This effect is formally treated
in the same way as molecular diffusion and the two influences are not separated.
Beginning with the classic experiments of Nielsen and Biggar (1961, 1962) and
Biggar and Nielsen (1962), soil physicists described the movement of dissolved
chemicals through soil using the so-called convection-dispersion equation.
ac a c ac 2
at =D az2 -V az +41, (1)

where C is solution concentration, D is the effective diffusion-dispersion coef-

ficient, V is the pore water velocity, and 41 is a general reaction term. Application
of this theory to N movement has been extensively reviewed by Gardner (1965).
Nitrogen reactions during movement through soil were studied by Cho (1971)
and in a series of papers by Misra et al. (1974 a-c). For simultaneous oxidation
ofNHt to NO; and reduction of NO; to gaseous N 2 , Misra et al. used a series
z, z
of first-order rate coefficients describing the NHt -+ NO NO -+ NO;, NO;
-+ N 2 reactions and solved for the rate coefficients by observing laboratory col-
umn breakthrough data. Recent work on denitrification has emphasized the in-
termediate N 2 0 state as well (Bremner and Blackmer 1978). A mathematical ap-
proach similar to that of Misra et al. (1974a-c) was used to study the transfor-
mations of urea N in soil columns by Wagenet et al. (1977).
Numerous laboratory studies have proved successful in describing leaching
processes for dissolved chemicals so that Eq. (1) is valid beyond question where
applied to inert solutes. However, when soil reactions are also involved, such as
adsorption or biological-chemical transformations, the interaction between flow
rate and adsorption kinetics is not well understood even in the laboratory. Under
equivalent flow conditions, however, the first-order rate coefficients obtained in
the above mentioned laboratory experiments and others have proven to be useful
for estimating the fate of NO; moving through soil columns.
Under field conditions, nonuniform water flow has created additional prob-
lems both in measurement and modeling of chemical movement. The first attempt
to apply the convection-dispersion Eq. (1) under large field conditions was con-
58 P.F. PrattandW.A.Jury

ducted by Biggar and Nielsen (1976) who measured a wide distribution of disper-
sion coefficients and water velocities when Eq. (1) was applied to NO;- movement
at different locations in the field. Similarly, Jury et al. (1976) found that a one-
dimensional model ofNO;- movement was not sufficient to describe NO;- leach-
ing under a potato crop and Cameron et al. (1979) found that spatial variations
due to differential rates of leaching caused by runoff and transport variability
created large differences between predictions using Eq. (1) and measurements.
However, Watts and Hanks (1978) found a good agreement with a model predict-
ing NO;- movement and uptake by corn using Eq. (1) together with a water model
and simple reaction terms similar to those discussed above.
Although only a limited number offield studies have been conducted, it is be-
coming apparent that nonuniform leaching patterns arising from variation in soil
physical properties create substantial difficulties for those who would model the
movement of dissolved chemicals such as NO;- through soil. At least near the sur-
face, these variations arise primarily from variations in water movement and
therefore will be resolved only when a better model for water velocity variations
is found. In recent years, several such approaches have emerged. Dagan and Bres-
ler (1979) used scaling theory together with a statistical model water input vari-
ability to describe chemical leaching across a field. Jury (1982) and Jury et al.
(1982) proposed a stochastic transfer function model for calibrating the water
flow variability from a single measurement. The calibration allows a later predic-
tion of chemical movement to be made in the region of calibration.
The management implications of such variability are largely unexplored at
this time. A recent discussion (Jury 1983) of differences in prediction between
stochastic and deterministic models such as Eq. (1) showed large differences in
predicted leaching behavior with substantial management implications for pollu-
tion. Under spatially variable field conditions, if an understanding is required of
the extreme behavior of a field, such as rapid leaching due to cracks, worm holes,
etc., then several of our existing management notions may have to be revised.
In spite of the absence of a useful general theory to predict movement of water
an NO;- flux through the unsaturated zone, calculations based on the piston flow
model can provide estimates of the approximate magnitude of flux rates and resi-
dence times for deep unsaturated zones in valleys filled with alluvium. The resi-
dence time is calculated from
SO
t=-
D'
where t is time in years, S is depth in em, 0 is the volumetric water content of
the soil materials through which the water is percolating, and D is the drainage
volume in cm yr- 1 • Assuming no cracks or channels through which the water
flows, Pratt et al. (1978) estimated flux rates of 0.5 to 3.0 m yr- 1 or residence
times of 10 to 60 years for a 30-m depth, based on data for nearly 100 irrigated
sites where deep soil cores were analyzed.
The amounts ofNO;- that leach from soil profiles (root zone) depends on the
amount of water (drainage volume) that moves through the profile, the NO;- in-
put, added to and produced in the profile, and the effectiveness of competing
reactions, i. e., assimilation by roots and by microorganisms and dissimilation by
 Pollution of the Unsaturated Zone with Nitrate 59

denitrification. Because of large ranges in NO;- input, assimilation and dissimi-

lation in various climate-soil-crop-management systems, a unique solution to
leaching ofNO;- is impossible. However, the collective competing reactions can
be expressed as an effective first-order reaction rate coefficient combined with wa-
ter flux to develop a conceptually useful model.
An approximate relationship between drainage volume and NO;- leached was
developed by analyzing a steady-state system under continuous irrigation. The as-
sumptions are: (1) uniform NO;- concentration (CJ in the irrigation water; (2)
uniform water uptake in the root zone over the depths 0 < Z < L, where L is the
depth to the bottom of the root zone; (3) an effective first-order reaction k (yr - 1)
for the sum of all reactions that compete with leaching (e. g., denitrification, plant
uptake); and (4) steady water flow with uniform water content and constant eva-
potranspiration, ET.
With these assumptions, the steady state drainage concentration is approxi-
mately

C(L t) = CONST = ~e-k«LF) (2)

, LF,'
where
L Odz LO
-r(LF) = Jo -Jw(z) = -In(I/LF),
ET
(3)

is the residence time for NO;- in the root zone and Jw(z) is the steady state water
flux at z.
The mass of NO;- leached in 1 year is calculated by

(4)

The expression in Eq. (3) may be simplified by noting that the drainage water flux
Jw(L) OET· LF/(1- LF) and using Eq. (2). Thus,

M = C1ET· t . (LF)K (5)

(I-LF) ,
where K=kL/ET.
If we set t = 1 year, we can plot annual drainage volume, C = J w(L)t against M
for different values of K. Note that since annual cumulative ET is the same for all
cases that LF and D are related by
D
LF=ET+D (6)

It is useful to notice that M is proportional to C1and to ET and that one obtains

the same curve for a given value of
K=kL/ET. (7)
Relationships between NO;- -N leached and drainage volume for various as-
sumed values of k, using L= 100 em, ET=80 cm yr-l, and C1=20 nig 1-1 are
60 P. F. Pratt and W. A. Jury

50r---------------?-------~~----~r_----~

40

7.... 30
>.
I
.s::
C ET=80em yr- I
L=IOOem
~ 20 C =20mg I-I
Z
k=2 yr- I

k=5 yr- I
30 40 50
D, em yr- I

Fig. 3. Relationship between NO; leached and drainage volume, D, calculated for a steady-state
model for various first-order reaction rates for competing reactions. ET was 80cm and C j was 20mg
NO;-Nl- 1

presented in Fig. 3. These curves reflect not only the effects of k values, but also
the effects of the residence time in the root zone. The longer the residence time,
the greater the amount of assimilation and dissimilation of NO; . For all curves,
a linear relationship between NO; leached and D could be used without a large
departure from the calculated lines when the D value is greater than 5 cm yr- 1 •
Thus, considering the scatter of data points that would be obtained from field
measurements, a linear relationship would be expected for any given set of soil,
climate, crop, and N and water management conditions where D is 5 cm yr- 1 or
larger. If the effective k value is > 1, the intercept for the linear relationship would
be negative and for k values <0.8, it would be positive. For values of 0.8 to 1.0,
the intercept would likely be near zero.
The relationships expressed in Fig. 3 are calculated for highly specific con-
ditions and should be considered only as qualitative indications of the effects of
water flux and rates of competitive reactions on leaching of NO; . However, they
do suggest that field measurements might produce linear relationships between
NO; leached and drainage volume and that negative intercepts might be found.
Data for the number of studies for which the relationships between NO;
leached from the root zone and drainage volume were possible are presented in
Table 1. In each case, there was no indication of curvilinearity in the data. The
linearity of the relationship and the range in intercepts indicate that the relation-
ships presented in Fig.3 have some value in qualitatively predicting the real
world. The correlation between the regression coefficient, the slope of the linear
relationship between M and D, and N fertilizer N inputs showed a significant
coefficient of 0.92, indicating that the effects of drainage volume are greater when
more NO; is in the soil system.
 Pollution of the Unsaturated Zone with Nitrate 61

Table 1. Regression and correlation between NO; -N leached, M, and drainage volume, D, for various
studies

Reference Conditions Regression Correlation

equation • coeffcient a
Fertilizer N Crop Drainage
kgha- 1 yr- 1

Letey et aI. Variable Various Tile M=- 4.5 +2.7 D 0.89

(1979) mean =430
Rible et aI. Variable Various Free M= 11.7 +3.0 D 0.77
(1979) mean =250
Nielsen et al. 0 Com Free M= - 2.5 +0.90D 0.90
(1979) 90 Com Free M=- 8.8 +1.3ID 0.98
180 Com Free M= -16.1 + 1.89D 0.97
360 Com Free M= -30.0 +4.15D 0.93
Robbins and 0 Various Free M= 6.0 +0.56D 0.92
Carter (1980) Crops following Various Free M= -45.0 +3.2 D 0.71
alfalfa plus
those that
received N
Pratt et aI. b 0 Barley- Free M=-48.0 +1.2 D -
(1976) sudangrass
400 Barley- Free M= 0.00+5.2 D -
sudangrass
750 Barley- Free M= 97.0 +5.1 D -
sudangrass

a All coefficients are significant at the 0.05 level except the vaIue 0.71, which approaches significance
at this level
b Not sufficient data points were determined to calculate correlation coefficients

4.6 Possible Solutions

Reductions in the amounts of NO; in the unsaturated zone will result from
improved efficiency of use of N by plants and by increased denitrification. In
some areas, management can be changed to increase denitrification. Raveh and
Avnimelech (1973) reduced the leaching of NO; , presumably because of denitri-
fication, as a result of increasing the saturated zone into the zone of micro biolog-
ical activity (root zone) in organic soils of the Hula Valley. Gilliam et al. (1979)
reduced the NO; leaching from poorly drained mineral soils by raising the water
table. In areas of waste disposal, denitrification can be increased by decreasing
aeration and by applications of easily decomposed organic materials.
However, in most croplands denitrification should be reduced along with
leaching losses. Both represent losses of a costly resource. Thus, in the vast ma-
jority of cropped fields, the solution is to manage for increased efficiency of use
of available N in the soil or to obtain high yields with smaller fertilizer N inputs.
The many direct and indirect factors involved in NO; leaching from the root
zone of cropped soils are illustrated in Fig.4. For a given land area with its soil,
climate, and surrounding economic conditions, the farmer has a limited number