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Several mathematical models have been developed to simulate processes and interactions in the plant rhizosphere. Most of these models are based on a rather simplified description of the soil chemistry and interactions of plant roots in the rhizosphere. In particular the feedback loops between exudation, water and solute uptake are mostly not considered, although their importance in the bioavailability of mineral elements for plants has been demonstrated. The aim of this work was to evaluate three existing coupled speciation-transport tools to model rhizosphere processes. In the field of hydrogeochemistry, such computational tools have been developed to describe acid-base and redox reactions, complexation and ion exchange, adsorption and precipitation of chemical species in soils and aquifers using thermodynamic and kinetic relationships. We implemented and tested a simple rhizosphere model with three geochemical computational tools (ORCHESTRA, MIN3P, and PHREEQC). Ó Springer Science+Business Media B.V. 2006analysis of the different solution strategies by comparing the numerical results to the analytical solution of solute uptake (K or Ca) by a single cylindrical root. All models are able to reproduce the concentration profiles as well as the uptake flux. The relative error of the simulated concentration profile decreases with increasing distance from the root. The uptake flux was simulated for all codes with less than 5% error for K and less than 0.4% for Ca. The strength of the codes presented in this paper is that they can also be used to investigate more complex and coupled biogeochemical processes in rhizosphere models. This is shown exemplarily with simulations involving both exudation and uptake and the simultaneous uptake of solute and water.

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There is evidence that degradation of pesticides in simple laboratory systems may differ from that in the field, but it is not clear which of the simplifications inherent in laboratory studies present serious shortcomings. Laboratory experiments evaluated several simplifying assumptions for a clay loam soil and contrasting pesticides. Degradation of cyanazine [2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropiononitrile] and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] at fluctuating temperature and moisture was predicted reasonably well based on parameters derived from degradation under constant conditions. There was a tendency for slower degradation of cyanazine and bentazone in soil aggregates of 3 to 5 mm in diameter (DT50 at 15 degrees C and 40% maximum water holding capacity of 25.1 and 58.2 d, where DT50 is the time for 50% decline of the initial pesticide concentration) than in soil sieved to <3 mm (DT50 of 19.1 and 37.6 d), but the differences were not significant for most datasets. Degradation of cyanazine, isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea], and chlorotoluron [3-(3-chloro-p-tolyl)-1,1-dimethylurea] was measured in soil amended with different amounts of lignin. The effect of lignin on degradation was small despite considerable differences in sorption. The DT50 values of cyanazine, isoproturon, and chlorotoluron were 16.2, 18.6, and 33.0 d, respectively, in soil without lignin and 19.0, 23.4, and 34.6 d, respectively, in soil amended with 2% lignin. Degradation of bentazone and cyanazine in repacked soil columns was similar under static and flow conditions with 50.1 and 47.2% of applied bentazone and 74.7 and 73.6% of applied cyanazine, respectively, degraded within 20 d of application. Thus, the assumptions underpinning laboratory to field extrapolation tested here were considered to hold for our experimental system. Additional work is required before general conclusions can be drawn.

Pesticide sorption in soils is controlled by time-dependent processes such as diffusion into soil aggregates and microscopic sorbent particles. This study examines the rate-controlling step for time-dependent sorption in clay loam aggregates. Aggregates (5 mm) were stabilized with alginate, and adsorption of azoxystrobin, chlorotoluron, and cyanazine was measured in batch systems equilibrated for periods between 1 h and 7 days. Stepwise desorption was measured at 1- or 3-day intervals following 1 or 7 days of adsorption. Time-dependent adsorption was also measured on dispersed soil. Results were interpreted using process-based modeling. Adsorption on dispersed soil was described by intraparticle sorption and diffusion. Adsorption in the aggregates was much less than in suspension, suggesting that part of the sorption capacity of the dispersed soil was not available within the aggregates (approximately 50%). Adsorption and desorption were reversible and could be described by pore diffusion into the aggregate with effective diffusion coefficients between 0.5 x 10(-10) and 1 x 10(-10) m2 s(-1), a factor 3-6 slower than estimated theoretically. Intraparticle diffusion did not seem to contribute to sorption in the aggregates at this time scale. Apparent hysteresis was explained by nonattainment of equilibrium during the adsorption and desorption steps.