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VII. Kinetics of Ionic Reactions in Heterogeneous Soil Systems

VII. Kinetics of Ionic Reactions in Heterogeneous Soil Systems

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thus, a partial layer collapse would occur (Sawhney, 1966). The observation

of slower desorption than adsorption suggests that potassium reactions are

nonsingular and that hysteresis could be occurring (Ardakani and McLaren,

1977;Rao and Davidson, 1978; Sparks et al., 1980b). Slow rates of potassium

desorption have also been noted by others (Talibudeen and Dey, 1968;

Feigenbaum and Levy, 1977).



Kinetic studies in soil systems have been investigated extensively with

phosphorus (Olsen and Khasawneh, 1980; Sharpley et al., 1981a,b). Amer et

al. (1955) studied the rate of phosphorus desorption from a soil suspension

using an anion exchange resin. They concluded that initial phosphorus

desorption increased very rapidly, then leveled off with time. Evans and

Jurinak (1976), using an anion exchange resin to simulate plant uptake of

released phosphorus, found that phosphate kinetics were characterized by

three simultaneous first-order rate expressions. Phosphate sorption interactions in a sandy soil were investigated by Fiskell et al. (1979). Phosphate

sorption was described by both a rapid and a slow reversible reaction which

occurred simultaneously at two separate types of sorption sites.



An extensive amount of literature is present on the kinetics of nitrogen

reactions in soils. This includes work on nitrification (Stevens and Reuss,

1975; Feigenbaum and Hadas, 1980; Tabatabai and Al-Khafaji, 1980),

denitrification (Stanford et al., 1975a; Kohl et al., 1976), and volatilization of

NH3 (Fenn et al., 1981, 1982).

Feigenbaum and Hadas (1980) found that the nitrification rate constant in

a sandy soil was slightly higher than that in a clay soil. This was ascribed to

the more favorable aeration conditions in the sandy soil. A decrease in

NH4-15N recovery in the soils with time during the first 20 days after

fertilization was exponential, indicating first-order kinetics of the nitrification

process. The rate constant was 0.13 day-' and the half-life of NH: in

the field was 5 days, which the authors noted was considerably higher than

reported in the literature for laboratory incubation experiments at similar


Many researchers have noted that the rate of denitrification in soils

conforms to zero-order kinetics (Patrick, 1960; Broadbent and Clark, 1965;

Keeney, 1973). Other workers have shown denitrification to follow first-order

kinetics (Bowman and Focht, 1974; Stanford et al., 1975a,b; Kohl et al.,



1976). Reddy et ul. (1978) suggested that the discrepancies in the above

findings could be ascribed to the failure of many researchers to consider the

presence of excessive overlying water. Reddy et al. (1978) found that the

process of denitrification followed zero-order kinetics when all the NO,-N

was present in the active soil layer and no excessive water was present.

However, when excessive water was present, NO; -N assumed an equilibria1

balance between the solid and solution phases and was denitrified by an

apparent first-order reaction. Reddy et al. (1978) attributed these phenomena

to enhanced rates of NO, reduction under conditions of excessive water.


There is a real need to better understand the kinetics of sulfur adsorption

and desorption in soils and clays. However, few reports appear in the

literature on this topic. Hackerman and Stephens (1954) investigated the

adsorption of sulfate ions from aqueous solutions by iron surfaces, while

Tripathi et al. (1975) investigated adsorption of sulfate ions on ignited

alumina. Rajan (1978) studied the adsorption of sulfate on hydrous alumina.

True kinetic studies of sulfate adsorption on soils are sparse indeed (Chang

and Thomas, 1963; Liu and Thomas, 1961).




The kinetics of exchange with trace elements and heavy metals in soils have

been investigated to only a limited extent. Griffin and Burau (1974),

investigating the kinetics of boron desorption from soil, showed that two

pseudo first-order reactions and one very slow reaction described the system

of exchange. It was assumed that the two reaction rates were due to binding

sites of varying reactivity in the soil. The two fast reactions were attributed to

release from Al-, Fe-, and Mg-hydroxy species in the clay fraction, while the

slow reaction was ascribed to diffusion of boron from the interlayers of clay

minerals. Evans and Sparks (unpublished data) investigated the kinetics of

boron sorption on horizons from seven soils from Delaware. The sorption

process conformed to a single first-order reaction in all of the soils. Apparent

boron sorption rate coefficients kh ranged from 0.029 to 0.129 min-'. The

total amount of boron sorbed/g of soil ranged from 3.14 x

to 1.39 x

mol/kg. The total amount of boron sorbed was strongly related to the

organic matter and clay contents of the soil horizons. Sorption-desorption

processes in the soil horizons exhibited marked hysteresis. The nonsingular

reactions were attributable to the organic matter content of the soil horizons.



The magnitude of reversibility increased with decreasing organic matter

levels. Bunzel et al. (1976), investigating the kinetics of heavy metals and trace

elements on peat, noted that for the given amounts of metal ions added to the

organic matter, the relative rate of adsorption decreased in the order of

Ca2+ > ZnZ+> CdZ+> Pb2+ > Cu2+. Since the ions used had diffusion

coefficients of similar value, the authors inferred that the ion with the highest

selectivity for peat would be the ion which was most rapidly adsorbed. The

quantity of metal ions desorbed by the hydronium ion (H,Q+) was too small

to predict reliable rate processes. Cavallaro and McBride (1978), working

with Cu2+ and CdZ+,showed rapid adsorption of these metals on selected

acid and calcareous soils. Salim and Cooksey (1980), investigating the

adsorption of PbZ+on river muds, found that the rate of exchange conformed

to first-order kinetics.


I thank Mrs. Cyndi Timko for typing this manuscript. Appreciation is also expressed to Ted

Carski, Jerry Hendricks, and Richard Ogwada for their helpful comments and suggestions. I

wish to dedicate this article with much love to my wife, Joy.


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Martin Alexander

Department of Agronomy

Cornell University

Ithaca. N e w York

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

11. Rhizobium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

111. Free-Living Heterotrophs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1v. Blue-Green Algae in Flooded Soils . . . . . . . . . . . . . . . . . . . . . . . . . . .

V. Resistant Isolates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

VI. Choice of Pesticides and Inocula . . . . . . . . . . . . . . . . . . . . . . . . . . . .

VII. Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

VIII. Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .











Under natural conditions, the presence of active nitrogen-fixing microorganisms is a necessary but often not a sufficient condition for significant

nitrogen fixation to occur. This is true of reactions brought about by

Rhizobium in association with leguminous plants, by a variety of bacterial

genera in the rhizosphere of cereals or other nonlegumes, or by blue-green

algae (cyanobacteria), which often proliferate in waterlogged soils planted

with rice. The lack of appreciable activity in regions where the microorganisms are naturally present and also in areas where they are deliberately added

by inoculation is often attributable to abiotic stresses that affect the survival,

proliferation, or metabolism of these organisms. However, recent evidence

suggests that the low activity may frequently be a result of biotic stresses,

specifically a consequence of interactions between the nitrogen fixers and

other microorganisms or lower animals. These harmful organisms prey or

graze upon or compete with the active species and thus potentially reduce the

amount of nitrogen introduced into agricultural or natural ecosystems. The

purpose of this review is to present evidence that these harmful predators,

grazers, or competitors can be controlled by pesticides and to suggest that

these chemicals may thus function not only to control pests but also, in an

indirect fashion, to effect a nitrogen gain in agricultural practice.


Copyright 0 1985 by Academic Press, Inc.

All rights of reproduction in any form reserved.



Inoculation with nitrogen-fixing microorganisms is known to cause nitrogen gains associated with the cultivation of legumes and sometimes cereals.

However, such inoculation often has only a small effect, at least compared

with the potential nitrogen gains that would occur if the microorganisms

were added to plants grown in sterile soil or to unplanted sterile flooded or

nonflooded soil. Often, the inoculum has no effect at all. In the case of

legumes, for example, inoculation with Rhizobium sometimes does not lead to

the appearance of nodules formed by the inoculum (Obaton, 1977), nodules

being required for nitrogen fixation by this symbiosis. In some cases, only

about 20% (Kuykendall and Weber, 1978) or as few as 5 % (Dobereiner,

1978) of the nodules are derived from the inoculum strain of Rhizobium, the

use of which is recommended because of the low nitrogen-fixation effectiveness of the indigenous rhizobia in the soil. Similarly, the poor ability of

Rhizobium to colonize the roots even of its host legumes is evident in the

benefit arising from large as compared to small inocula applied to clover

(Holland, 1970) and soybeans (Kapusta and Rouwenhorst, 1973).

Extensive colonization of the rhizosphere of legumes by effective strains of

Rhizobium, of the root zone of nonlegumes by free-living nitrogen-fixing

bacteria, and of flooded soils and the overlying water is necessary for nitrogen

gains to be extensive. This is true for both indigenous nitrogen fixers and

organisms used as inocula. In the case of Rhizobium, the degree of colonization when roots are susceptible to infection is reflected in the extent of

nodulation. Thus, a threshold number of the root-nodule bacteria appears to

be necessary for nodulation to occur (Bohlool and Schmidt, 1973; Purchase

and Nutman, 1957), and the abundance of nodules is directly related to the

number of rhizobia in the root zone (Lim, 1963). For the free-living bacteria

and blue-green algae, the extent of nitrogen accretion is likely a direct

function of the extent of growth because a small biomass probably brings

about little nitrogen input and growth is required for the initially small

population in the soil or the inoculum to give the large cell mass necessary for

significant activity. This colonization requires that the active species attain or

maintain large populations in environments with numerous competitors,

many of which grow faster, as well as protozoa that prey on them and

invertebrates that graze on them.

Despite the abundance and activity of competitors, predators, and other

organisms that may be inimical to the nitrogen fixers, few attempts have been

made to favor the inoculum organism in some selective way. The inoculum

strain is added to the seed, the floodwater, or sometimes the soil, and in the

absence of a means of selective stimulation, large inocula are used. Even

many of these large inocula are of little value. In contrast, the approach

suggested here is designed to overcome the natural biotic stresses or

biological controls that hold the nitrogen fixers in check. The approach

involves (1) first establishing the importance of predation, competition, or

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