Pesticide Sorption and Desorption Kinetics

Pesticide Sorption and Desorption Kinetics 129 Classes of Pesticides 129 Reaction Rates 130... 

PESTICIDE SORPTION AND DESORPTION KINETICS Classes of Pesticides... 

Karickhoff (1980) and Karickhoff et al. (1979) have studied sorption and desorption kinetics of hydrophobic pollutants on sediments. Sorption kinetics of pyrene, phenanthrene, and naphthalene on sediments showed an initial rapid increase in sorption with time (5-15 min) followed by a slow approach to equilibrium (Fig. 6.7). This same type of behavior was observed for pesticide sorption on soils and soil constituents and suggests rapid sorption on readily available sites followed by tortuous diffusion-controlled reactions. Karickhoff et al. (1979) modeled sorption of the hydrophobic aromatic hydrocarbons on the sediments using a two-stage kinetic process. The chemicals were fractionated into a labile state (equilibrium occurring in 1 h) and a nonlabile state. 

Sorbed pesticides are not available for transport, but if water having lower pesticide concentration moves through the soil layer, pesticide is desorbed from the soil surface until a new equiUbrium is reached. Thus, the kinetics of sorption and desorption relative to the water conductivity rates determine the actual rate of pesticide transport. At high rates of water flow, chances are greater that sorption and desorption reactions may not reach equihbrium (64). NonequiUbrium models may describe sorption and desorption better under these circumstances. The prediction of herbicide concentration in the soil solution is further compHcated by hysteresis in the sorption—desorption isotherms. Both sorption and dispersion contribute to the substantial retention of herbicide found behind the initial front in typical breakthrough curves and to the depth distribution of residues. 

Many of the early studies on kinetics of soil chemical processes were obviously concerned with diffusion-controlled exchange phenomena that had half-lives (r1/2) of 1 s or greater. However, we know that time scales for soil chemical processes range from days to years for some weathering processes, to milliseconds for degradation, sorption, and desorption of certain pesticides and organic pollutants, and to microseconds for surface-catalyzed like reactions. Examples of the latter include metal sorption-desorption reactions on oxides. 

The rate of sorption and desorption of pesticides on soils and soil constituents has been investigated by a number of workers (see, e.g., Hance, 1967) and is dependent on the type of sorbent, pesticide, and rate of mixing. For example, sorption seems much slower on humic substances (Khan, 1973). Other factors that may affect the kinetics are swelling of the sorbent and temperature (Hance, 1967). 

Johnston AE, Goulding KWT, Poulton PR (1986) Soil acidification during more than 100 years under permanent grassland and woodland at Rothamsted. Soil Use Manage 2 3-10 Kahn SU (1982) Bound pesticides residues in soil and plant. Residue Rev 84 1-25 Kan AT, Chen W, Tomson MB (2000) Desorption kinetics from neutral hydrophobic organic compounds from field contaminated sediment. Environ Pollution 108 81-89 Kang SH, Xing BS (2005) Phenanthrene sorption to sequentially extracted soil humic acids and humans. Environ Sci Technol 39 134-140... 

Another important consideration in investigation of the reaction of sorbed pesticides is the nature of the sorption process itself. Sorption/desorption kinetics and the physicochemical characteristics of the pesticide molecules in the sediment-sorbed state can be expected to influence the kinetic observations made in experimental systems. 

Scow, K. M. (1993)- Effect of sorption-desorption and diffusion processes on the kinetics of biodegradation of organic chemicals in soil. In Sorption and Degradation of Pesticides and Organic Chemicals in Soil, ed. D. M. Linn, T. H. Carski, M. L. Brusseau F-H. Chang, pp. 73-114. Madison, WI Soil Science Society of America, American Society of Agronomy. 

Unfortunately, our present understanding of sorption kinetics is inadequate to allow unambiguous representation of the sorption-desorption process. Clearly the states of sorbed pesticides include fractions which vary in their lability with respect to desorption (9. 10, 21). The fraction of the sorbed molecules in relatively labile and non-labile states is a function of the nature of the pesticide and sediment and the time of contact between the sediment and pesticide solution. 

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