Pesticides kinetics

FIG. 1. Scheme of potential factors in placenta that affect (he iransplacemal transfer anti ensuing effects on placenta and fetus. Although very little is known about (he role of transporters, metabolizing enzymes, binding proteins, and cellular targets in pesticide kinetics and dynamics, there are a number of cxperimemal tools available for the elucidation of these factors. 

Kinetics of Pesticide Biodegradation. Rates of pesticide biodegradation are important because they dictate the potential for carryover between growing seasons, contamination of surface and groundwaters, bio accumulation in macrobiota, and losses of efficacy. Pesticides are typically considered to be biodegraded via first-order kinetics, where the rate is proportional to the concentration. Figure 2 shows a typical first-order dissipation curve. 

For those pesticides that are cometabolized, ie, not utilized as a growth substrate, the assumption of first-order kinetics is appropriate. The more accurate kinetic expression is actually pseudo-first-order kinetics, where the rate is dependent on both the pesticide concentration and the numbers of pesticide-degrading microorganisms. However, because of the difficulties in enumerating pesticide-transforming microorganisms, first-order rate constants, or half-hves, are typically reported. Based on kinetic constants, it is possible to rank the relative persistence of pesticides. Pesticides with half-hves of <10 days are considered to be relatively nonpersistent pesticides with half-hves of >100 days are considered to be relatively persistent. 

For those pesticides which are utilized as microbial growth substrates, sigmoidal rates of biodegradation are frequentiy observed (see Fig. 2). Sigmoidal data are more difficult to summarize than exponential (first-order) data because of their inherent nonlinearity. Sigmoidal rates of pesticide metabohsm can be described using microbial growth kinetics (Monod) however, four kinetics constants are required. Consequentiy, it is more difficult to predict the persistence of these pesticides in the environment. 

Carboxyhc acid ester, carbamate, organophosphate, and urea hydrolysis are important acid/base-catalyzed reactions. Typically, pesticides that are susceptible to chemical hydrolysis are also susceptible to biological hydrolysis the products of chemical vs biological hydrolysis are generally identical (see eqs. 8, 11, 13, and 14). Consequentiy, the two types of reactions can only be distinguished based on sterile controls or kinetic studies. As a general rule, carboxyhc acid esters, carbamates, and organophosphates are more susceptible to alkaline hydrolysis (24), whereas sulfonylureas are more susceptible to acid hydrolysis (25). 

Many factors affect the mechanisms and kinetics of sorption and transport processes. For instance, differences in the chemical stmcture and properties, ie, ionizahility, solubiUty in water, vapor pressure, and polarity, between pesticides affect their behavior in the environment through effects on sorption and transport processes. Differences in soil properties, ie, pH and percentage of organic carbon and clay contents, and soil conditions, ie, moisture content and landscape position climatic conditions, ie, temperature, precipitation, and radiation and cultural practices, ie, crop and tillage, can all modify the behavior of the pesticide in soils. Persistence of a pesticide in soil is a consequence of a complex interaction of processes. Because the persistence of a pesticide can govern its availabiUty and efficacy for pest control, as weU as its potential for adverse environmental impacts, knowledge of the basic processes is necessary if the benefits of the pesticide ate to be maximized. 

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. 

An enzymatic assay can also be used for detecting anatoxin-a(s). " This toxin inhibits acetylcholinesterase, which can be measured by a colorimetric reaction, i.e. reaction of the acetyl group, liberated enzymatically from acetylcholine, with dithiobisnitrobenzoic acid. The assay is performed in microtitre plates, and the presence of toxin detected by a reduction in absorbance at 410 nm when read in a plate reader in kinetic mode over a 5 minute period. The assay is not specific for anatoxin-a(s) since it responds to other acetylcholinesterase inhibitors, e.g. organophosphoriis pesticides, and would need to be followed by confirmatory tests for the cyanobacterial toxin. 

Lartiges SB, Garrigues PP. 1995. Degradation kinetics of organophosphorus and organonitrogen pesticides in different waters under various environmental conditions. Environ Sci Technol 29 1246-1254. 

Singh NC, TP Dasgupta, EV Roberts, A Mansingh (1991) Dynamics of pesticides in tropical conditions. 1. Kinetic studies of volatilization, hydrolysis, and photolysis of dieldrin and a- and b-endosulfan. J Agric Food Chem 39 575-579. 

Although the improved extraction kinetics also increase the concentration of coextractives in the final extract, some degree of selectivity can be achieved by careful selection of the solvent or solvents used. Matrix co-extractives may be removed, or at least partially removed, by placing a suitable sorbent, such as alumina, at the exit of the extraction cell to remove lipid co-extractives. Excellent recoveries of both polar and nonpolar pesticides from a wide range of foodstuffs have been reported. Specific applications include organophosphorus and A-methylcarbamate pesticides. 

What materials are likely to contain pesticide residues following application What are the known degradation kinetics of the crop protection product being evaluated ... 

Duration and route of exposure can influence the interpretation of biological markers for instance, in some cases, pesticides that are inhaled remain in systemic circulation longer than those that are ingested. Compounds characterized by a slow process of dermal absorption can give rise to prolonged kinetics if compared to the kinetics following ingestion or inhalation of the same compounds. 

Adsorption and desorption. The user can choose to handle this using either temperature-corrected first order reaction kinetics, in which case the concentrations are always moving towards equilibrium but never quite reach it, or he can use a Freundlich isotherm, in which instantaneous equilibrium is assumed. With the Freundlich method, he can elect either to use a single-valued isotherm or a non-single-valued one. This was included in the model because there is experimental evidence which suggests that pesticides do not always follow the same curve on desorption as they do on adsorption. 

Simple models are used to Identify the dominant fate or transport path of a material near the terrestrial-atmospheric Interface. The models are based on partitioning and fugacity concepts as well as first-order transformation kinetics and second-order transport kinetics. Along with a consideration of the chemical and biological transformations, this approach determines if the material is likely to volatilize rapidly, leach downward, or move up and down in the soil profile in response to precipitation and evapotranspiration. This determination can be useful for preliminary risk assessments or for choosing the appropriate more complete terrestrial and atmospheric models for a study of environmental fate. The models are illustrated using a set of pesticides with widely different behavior patterns. 

M. Ayyagari, S. Kametkar, R. Pande, K.A. Marx, J. Kumar, S.K. Tripathy, J. Akkara, and D.L. Kaplan, Chemiluminescence-based inhibition kinetics of alkaline phosphatase in the development of a pesticide biosensor. Biotechnol. Prog. 11, 699-703 (1995). 

Bakthavathsalam, R. and Y.S. Reddy. 1981. Lipid kinetics in relation to the toxicity of three pesticides in the climbing perch, Anabas testudineus (Bloch). Proc. Indian Natl. Sci. Acad. B47 670-676. 

Thust, R., Mendel, J., Schwarz, H. and Warzoki, R. (1980). Nitrosated urea pesticide metabolites and other nitrosamides. Activity in clastogenicity and SCE assays, and aberration kinetics in Chinese hamster V79-E cells. Mutation Res. 79 239-248. 

Direct kinetic assays are the only valid methods for the measurement of activators and inhibitors and calibration plots of the percentage activation or inhibition by known amounts of the substance can be made. Examples of inhibition assays include the quantitation of organophosphorus pesticides using the inhibition of cholinesterase (EC 3.1.1.7) while manganese can be measured in amounts as low as 1 X 10-12 mol using its activating effect on isocitrate dehydrogenase (EC 1.1.1.41). 

This project was designed to demonstrate that the static water model ecosystems can be scaled up in size to provide sufficient amounts of biomass, soil, and water to study metabolism kinetics of pesticides. Fourteen kg of soil, treated with [l C]-trifluralin at 10 ppm, was flooded with 84 liters water. Blue-gill fish, snails, daphnids, and algae were exposed to this system for 72 days. Samples of soil, water, and organisms were periodically analyzed for trifluralin and eight metabolites. 

Abstract Removal of the pesticide metobromuron from aqueous solutions by adsorption at the high area activated carbon cloth was investigated. Kinetics of adsorption was followed and adsorption isotherms of the pesticide was also be determined. In kinetic studies a special V-shaped cell with an UV cuvette attached to it was used for adsorption processes. With this cell it was possible to follow the concentration of pesticide molecule by in situ UV spectroscopy as it is adsorbed at the activated carbon cloth. The obtained absorbance vs time data were converted into concentration vs time data and these data were treated according to pseudo-first-order and psendo-second-order kinetic models. Adsorption of that pesticide was fonnd to follow second-order kinetic model with k 87.35 g mol min. Adsorption isotherms were derived at 25°C on the basis of batch analysis. Isotherm data were treated according to Langmuir and Freundlich models. The fits of experimental data to these equations were examined and founded that the adsorption isotherm was well represented by Frenndlich model. 

Keywords Activated carbon, isotherm, kinetics, metobromuron, pesticide... 

In order to obtain the calibration curve of pesticide metobromuron, absorbances were measured at the corresponding as a function of concentration and the data were fitted to Lambert-Beer law by the method of least square analysis. The resulting correlation coefficient (R 1.0000) show that the fit to Lambert-Beer law is excellent. The obtained calibration equation was used to convert absorbances into concentrations in kinetic and equilibrium studies. 

Adsorption kinetic and adsorption isotherm of pesticide metobromuron at the high area ACC were investigated in relation to water treatment. The ACC used in this study seems to be quite effective in adsorption of metobromnron from aqueous solutions. Adsorption of that pesticide was found to follow second-order kinetic model and the adsorption isotherm is well represented by Frenndlich model. 

Bachman, J. and Patterson, H.H. Photodecomposition of the carbamate pesticide carbofuran kinetics and the influence of dissolved organic matter. Environ. Sci. Technol, 33(6) 874-881, 1999. 

Legierse, K.C.H.M., Sijm, D.T.H.M., van Leeuwen, C.J., Seinen, W., and Mermens, J.L.M. Bioconcentration kinetics of chlorobenzenes and the organophosphorus pesticide chlorthion in the pond snail Lymnaea stagnalis n comparison with the guppy Poecilia reticulata, Aquat. Toxicol., 41(3) 301-323, 1998. 

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... 

Sparks DL (ed) (1986) Soil physical chemistry. CRC Press, Boca Raton, Florida Sparks DL (1989) Kinetics of soil processes. Academic Press, San Diego Sparks DL, Huang PM (1985) Physical chemistry of soil potassium. In Munson RE (ed) Potassium in agriculture, ASA, Madison, Wisconsin, pp 201-276 Sparks DL, Jardine PM (1984) Comparison of kinetic equations to describe K-Ca exchange in pure and mixed systems. Soil Sci 138 115-122 Spencer WF, Cliath MM (1969) Vapor densities of dieldrin. Environ Sd Technol 3 670-674 Spencer WF, Chath MM (1973) Pesticide volatilization as related to water loss from soil. J Environ Qual 2 284-289... 

Recently reported results for the hydrolysis kinetics of chlorpyrifos (7 ) suggest that equation 2 may not be a valid representation of alkaline hydrolysis kinetics for at least one class of pesticides (organophosphorothioates). In short, kg may be pH dependent. However, disappearance kinetics for such molecules are still adequately described at fixed pH by pseudo first-order kinetics. 

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. 

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