Tải bản đầy đủ - 0trang
VII. Kinetics of Ionic Reactions in Heterogeneous Soil Systems
DONALD L. SPARKS
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.,
KINETICS OF IONIC REACTIONS
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.
DONALD L. SPARKS
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.
Aharoni, C., and Ungarish, M. 1976. J. Chem. Soc. Faraday Trans. 72,400-408.
Akratanakul, S., Boersma, L., and Klock, G. 0. 1983. Soil Sci. 135, 331-341.
Amer, F., Bouldin, D. R., Black, C. A,, and Duke, F. R. 1955. Plant & Soil 6, 391-394.
Ardakani, M. S., and McLaren, A. D. 1977. Soil Sci. Soc. Am. J. 41,877-879.
Atkinson, R. J., Hingston, F. J., Posner, A. M., and Quirk, J. P. 1970. Nature (London) 226,
Atkinson, R. J., Posner, A. M., and Quirk, J. P. 1972. J. Inorg. Nucl. Chem. 34, 2201-2211.
Ayodele, O., and Agboola, A. A. 1981. Soil Sci. SOC.Am. J. 45, 462-464.
Barrow, N. J. 1983. Fert. Res. 40, 41-59.
Barrow, N. J., and Shaw, T. C. 1979. J. Soil Sci. 30,67-76.
Bolt, G. A., Sumner, M. E., and Kamphort, A. 1963. Soil Sci. SOC.Am. Proc. 27, 294-299.
Bowman, R. A., and Focht, D. D. 1974. Soil Biol. Biochem. 6,297-301.
Boyd, G . E., Adamson, A. W., and Myers, L. S., Jr. 1947. J. Am. Chem. Soc. 69,2836-2848.
Broadbent, F. E., and Clark, F. 1965. In “Soil Nitrogen” (W. V. Bartholomew and F. E. Clark,
eds.), pp. 344359. Am. SOC.of Agron., Madison, WI.
Brown, J. L. 1981. Soil Sci. SOC.Am. J. 45,475-477.
Bunzel, K., Schmidt, W., and Sansoni, B. 1976. J. Soil Sci. 27, 32-41.
Burns, A. F., and Barber, S. A. 1961. Soil Sci. SOC.Am. Proc. 25, 349-352.
Carski, T. H., and Sparks, D. L. 1985. Appl. Clay Sci. 1, in press.
Cavallaro, N., and McBride, M. B. 1978. Soil Sci. Soc. Am. J. 42, 550-556.
Chang, M. L., and Thomas, G. W. 1963. Soil Sci. SOC.Am. Proc. 21, 281-283.
Chien, S. H., Clayton, W. R., and McClellan, G. H. 1980. Soil Sci. SOC.Am. J. 44, 260-264.
Chute, J. H., and Quirk, J. P. 1967. Nature (London) 213, 1156-1157.
Crank, J. 1976. “The Mathematics of Diffusion.” Oxford Univ. Press, London and New York.
Deist, J., and Talibudeen, 0. 1967. J. Soil Sci. 18, 125-137.
KINETICS OF IONIC REACTIONS
Evans, R. L., and Jurinak, J. J. 1976. Soil Sci.121, 205-21 1.
Eyring, H., Lin, S. H., and Lin, S. H. 1980. “Basic Chemical Kinetics.” Wiley, New York,
Feigenbaum, S., and Hadas, A. 1980. Soil Sci. SOC.Am. J. 44, 1006-1010.
Feigenbaum, S., and Levy, R. 1977. Geoderma 19, 159-169.
Fenn, L. B., Matocha, J. E., and Wu, E. 1981. SoilSci. Soc. Am. J. 45, 883-886.
Fenn, L. B., Matocha, J. E., and Wu, E. 1982. SoilSci. Soc. Am. J. 46, 78-81.
Fiskell, J. G. A., Mansell, R. S., Selim, H. M., and Martin, F. G. 1979. J. Environ. Qual. 8,579-584.
Frost, A. A., and Pearson, R. G. 1961. “Kinetics and Mechanism.” Wiley, New York.
Gedroiz, K. K. 1914. Zhur. Ophr. Agron. 15, 181-208.
Glasstone, S., Laidler, K. J., and Eyring, H. 1941. “The Theory of Rate Processes.” McGraw-Hill,
Goulding, K. W. T. 1983. Adv. Agron. 36, 215-264.
Griffin, R. A., and Burau, R. G. 1974. SoilSci. Soc. Am. Proc. 38,892-897.
Griffin, R. A., and Jurinak, J. J. 1974. Soil Sci. SOC.Am. Proc. 38, 75-79.
Hackerman, N., and Stephens, S. J. 1954. J. Phys. Chem. 58,904-908.
Hague, R., and Sexton, R. 1968. J. Colloid Interface Sci. 27, 818-823.
Hammes, G. G. 1978. “Principles of Chemical Kinetics.” Academic Press, New York.
Harter, R. D., and Lehmann, R. G. 1983. Soil Sci. SOC.Am. J. 41,666-669.
Helfferich, F. 1962. “Ion Exchange.” McGraw-Hill, New York.
Hingston, F. J. 1981. In “Adsorption of Inorganics at Solid-Liquid Surfaces” (M. A. Anderson
and A. J. Rubin, eds.), pp. 51-90. Ann Arbor Science, Ann Arbor, MI.
Hissink, D. J. 1924. Trans. Faraday Soc. 20, 551 -566.
Ismail, F. T., and Scott, A. D. 1972. SoilSci. Soc. Am. Proc. 36, 506-510.
Jardine, P. M., and Sparks, D. L. 1984a. Soil Sci. Soc. Am. J. 48,39-45.
Jardine, P. M., and Sparks, D. L. 1984b. Soil Sci. Soc. Am. J . 48,45-50.
Keay. J., and Wild, A. 1961. Soil Sci. 92, 54-60.
Keeney, D. R. 1973. J. Environm. Qual. 2, 15-29.
Kelley, W. P. 1948. “Cation Exchange in Soils.” Van Nostrand-Reinhold, Princeton, NJ.
Kohl, D. H., Vithayathil, F., Whitlow, R., Shearer, G., and Chien, S. H. 1976. SoilSci.SOC.Am. J.
Komareni, S. 1978. Soil Sci. Soc. Am. J . 42, 531-532.
Kuo, S., and Lotse, E. G. 1972. Soil Sci.Soc. Am. Proc. 36,725-729.
Kuo, S., and Lotse, E. G. 1974. Soil Sci. Soc. Am. Proc. 38, 50-54.
Kyle, J. H., Posner, A. M., and Quirk, J. P. 1975. J. Soil Sci. 26, 32-42.
Laidler, K. J. 1965. “Chemical Kinetics.” McGraw-Hill, New York.
Li, W. C., Armstrong, D. E., Williams, J. D. H., Harris, R. F., and Syers, J. K. 1972. Soil Sci. Soc.
Am. Proc. 36, 279-285.
Liu, M., and Thomas, G. W. 1961. Nature (London) 192, 384.
Low, M. J. D. 1960. Chem. Rev. 60, 267-271.
Malcom, R. L., and Kennedy, V. C. 1969. Soil Sci. Soc. Am. Proc. 33,245-253.
Martin, H. W., and Sparks, D. L. 1983. Soil Sci. SOC.Am. J. 47,883-887.
Mortland, M. M. 1958. Soil Sci. Soe. Am. Proc. 22, 503-508.
Murali, V., and Aylmore, L. A. G. 1981. A w f .J. Soil Rex 19, 23-29.
Murali, V., and Aylmore, L. A. G. 1983a. Soil Sci. 135, 143-150.
Murali, V., and Aylmore, L. A. G. 1983b. Soil Sci. 136, 279-290.
Neuman, W. F., and Neuman, M. W. 1958. “The Chemical Dynamics of Bone Mineral.” Univ.
Chicago Press, Chicago.
Olsen, S. R., and Khasawneh, F. E. 1980. In “The Role of Phosphorus in Agriculture” (F. E.
Khasawneh, E. C. Sample, and E. J. Kamprath, eds.), pp. 361-410. Amer. SOC.of Agronomy,
DONALD L. SPARKS
Onken, A. B., and Matheson, R. L. 1982. Soil Sci. Soc. Am. J . 46, 276-279.
Parravano, G., and Boudart, M. 1955. In “Advances in Catalysis” (W. G. Frankenburg, V. I.
Kamarewsky, and E. K. Rideal, eds.), pp. 47-62. Academic Press, New York.
Patrick, W. H., Jr. 1960. Int. Congr. Soil Sci. Trans., 7th 2, 494-500.
Probert, M. E., and Larsen, S. 1972. J. Soil Sci.23, 76-80.
Quirk, J. P., and Chute, J. H. 1968. lnt. Congr. Soil Sci. Trans., 9th 2, 671-681.
Rajan, S. S. S. 1978. Soil Sci. SOC.Am. J. 42, 39-44.
Rao, P. S. C., and Davidson, J. M. 1978. Soil Sci. Soc. Am. J. 42, 668.
Reddy, K. R., Patrick, W. H., Jr., and Phillips, R. E. 1978. Soil Sci. SOC.Am. J. 42, 268-272.
Reed, M. G., and Scott, A. D. 1962. Soil Sci. Soc. Am. Proc. 26,437-440.
Reichenberg, D. 1957. In “Ion Exchanges in Organic and Biochemistry”(C. Calmon and L. R. E.
Kressman, eds.), pp. 66-85. Wiley (Interscience), New York.
Salim, R., and Cooksey, B. G. 1980. Plant & Soil 54,399-417.
Sawhney, B. L. 1966. Soil Sci. Soc. Am. Proc. 30, 565-569.
Selim, H. M., Mansell, R. S., and Zelazny, L. W. 1976. Soil Sci. 122, 77-84.
Sharpley, A. N. 1983. Soil Sci. Soc. Am. J. 47,462-467.
Sharpley, A. N., Ahuja, L. R., and Menzel, R. G. 1981a. J. Enuiron. Quul. 10, 386-391.
Sharpley, A. N., Ahuja, L. R., Yamamoto, M., and Menzel, R. G. 1981b. SoilSci. Soc. Am. J. 45,
Sivasubramaniam, S., and Talibudeen, 0. 1972. J. Soil Sci. 23, 163-176.
Sparks, D. L. 1985. “Soil Physical Chemistry.” CRC Press, Boca Raton, FL, in press.
Sparks, D. L., and Jardine, P. M. 1981. Soil Sci. Soc. Am. J. 45, 1094-1099.
Sparks, D. L., and Jardine, P. M. 1984. Soil Sci. 138, 115-122.
Sparks, D. L., and Rechcigl, J. E. 1982. Soil Sci. Soc. Am. J. 46, 875-877.
Sparks, D. L., Zelazny, L. W., and Martens, D. C. 1980a. Soil Sci. SOC.Am. J. 44, 37-40.
Sparks, D. L., Zelazny, L. W., and Martens, D. C . 1980b. Soil Sci. Soc. Am. J. 44, 1205-1208.
Sposito, G. 1981a. “The Thermodynamics of Soil Solutions.” Oxford Univ. Press, London and
Sposito, G. 1981b. In “Chemistry in Soil Environment” (R. H. Dowdy, J. A. Ryan, V. V. Volk,
and D. E. Baker, eds.), pp. 13-30. (Amer. SOC.Agron. Spec. Publ. No. 40).
Stanford, G., Vanderpol, R. A., and Dzienia, S. 1975a. Soil Sci. SOC.Am. Proc. 39, 284-289.
Stanford, G., Dzienia, S., and Vanderpol, R. A. 1975b. Soil Sci. Soc. Am. Proc. 39, 867-870.
Stevens, R. G., and Reuss, J. 0. 1975. SoilSci. Soc. Am. Proc. 39, 787-793.
Tabatabai, M. A., and Al-Khafaji, A. A. 1980. Soil Sci. SOC.Am. J. 44, 1000-1006.
Talibudeen, O., and Dey, S. K. 1968. J. Agric. Sci. (Camb.) 71, 95-104.
Tamers, M., and Thomas, H. C. 1960. J. Phys. Chem. 64,29-32.
Thomas, G . W. 1977. Soil Sci. SOC.Am. Meet., Houston.
Thompson, H. S. 1850. J . R. Agric. SOC. Engl. 11, 68-74.
Tripathi, P. S. M., Tripathi, R., and Prasad, B. B. 1975. Proc. Indian Natl. Sci. Acad. 41, 156-159.
Ungarish, M., and Aharoni, C. 1981. J. Chem. Soc. Faraday Trans. 1,975-979.
Van Riemsdijk, W. H. 1970. Ph.D. thesis, Agricultural University, Wageningen.
Van Riemsdijk, W. H., and DeHaan, F. A. M. 1981. Soil. Sci. SOC.Am. J. 45,261-266.
Way, J. T. 1850. J . R. Agric. Soc. Engl. 11, 313-379.
White, R. E. 1976. Phosphorus Agric. 67, 9-14.
Zasoski, K. J., and Burau, R. G. 1978. Soil Sci. Soc. Am. J. 42, 372-374.
ADVANCES IN AGRONOMY. VOL 38
ENHANCING NITROGEN FIXATION
BY USE OF PESTICIDES: A REVIEW
Department of Agronomy
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