Exchange of Gaseous Nitrogen Compounds 449
Adsorption of NH
3
and fixation of NH
4
onto clay particles is typically regulated
by soil organic matter content and the type of clay minerals in the soil. Adsorption is
related to the surface area of the sorbing material and generally clay soils sorb more
NH
3
than do sandy soils ( Terman, 1979 ). The rate of NH
3
volatilization may be con-
trolled by the rate of removal and dispersion of NH
3
into the atmosphere by chang-
ing the concentration of NH
4
or NH
3
in the soil solution or by displacing any of the
equilibria as in Eq. 1 . The driving force for NH
3
volatilization from soil solution is
the difference in the NH
3
partial pressure between that in equilibrium with the liquid
phase and that in the ambient atmosphere. The equilibrium vapor pressure of NH
3
is controlled by the NH
3
concentration in adjacent solutes which, in the absence of
other ionic species, is affected by NH
4
ion concentration and pH. At pH 9.2 a solu-
tion contains approximately equal amounts of solution NH
4
and solution NH
3
. At
pH 7.2 the solution contains ⬃ 99% solution NH
4
and 1% solution NH
3
. Thus, NH
3
emissions are typically higher in more basic soils. Chemical equilibria dictate that
an aqueous solution will hold less NH
3
with increasing temperature, so temperature
affects soil–atmosphere NH
3
exchange as well ( Freney et al., 1983 ).
Ammonia must be transported to the soil surface before it can be lost to the
atmosphere. As a result, NH
3
losses are typically reduced by subsurface application
of fertilizers ( Terman, 1979 ). Ammonia transport can be accomplished by move-
ment in liquid or gaseous phases and their relative importance depends on soil water
content. Volatilization of NH
3
from solution at the soil surface occurs in response to
a difference in vapor pressure between solution and ambient air. Increasing wind
speed increases the rate of volatilization by permitting more rapid transport of NH
3
away from the water surface ( Freney et al., 1983 ).
Factors which influence soil–atmosphere NH
3
exchange include soil cation
exchange capacity (CEC), soil pH, soil buffer capacity, and calcium carbonate con-
tent. As NH
4
is positively charged it readily reacts with the soil cation exchange
complex. The disassociation of ammonium ion releases a proton in addition to NH
3
.
Consequently as NH
3
loss proceeds, the solution becomes acidified and as the frac-
tion of ammoniacal N is reduced an equilibrium is reached. For this reason NH
3
volatilization is generally not important in soils that have a high base saturation
( Freney et al., 1983 ). A strong correlation between NH
3
loss and calcium carbonate
content of soils has been observed ( Fenn et al., 1981 ). The apparent stimulation of
NH
3
volatilization has been related to soil clay-sized calcium carbonate content and
the formation of calcium fluoride, sulfate, and phosphate precipitates, and ammo-
nium bicarbonate ( Fenn et al., 1981 ; Terman, 1979 ).
NH
3
Volatilization from Surface Residues . Since NH
3
emissions are readily
reduced by placing ammonium-based fertilizers below the soil surface, surface appli-
cation of fertilizers can lead to increased NH
3
losses ( Terman, 1979 ). Increased use
of no-till management could contribute to this increase if new fertilizer N manage-
ment tools are not developed. An example of the impact of crop residue management
on NH
3
loss is the practice of trash retention following green cane harvesting in sugar
cane production. As practiced in north Queensland, Australia, cane trash is left on the
CH13-P374347.indd 449CH13-P374347.indd 449 5/31/2008 6:17:00 PM5/31/2008 6:17:00 PM