Interpretation of aged sorption studies for pesticides and their use in European Union regulatory leaching assessments.

First-tier regulatory exposure assessments for pesticides assume that pesticide sorption is instantaneous and fully reversible. In European Union (EU) regulatory guidance, an increase in sorption over time ("aged sorption") can be considered at the higher tier to refine predicted environmental concentrations in groundwater. Research commissioned by the UK Chemicals Regulation Directorate (CRD), funded by the Department for Environment Food & Rural Affairs (Defra), formed the basis of a draft regulatory guidance document proposing 1) a protocol on how to measure aged sorption of parent compounds in laboratory studies, 2) procedures to fit kinetic models to the experimental data, 3) criteria to test the reliability of the parameters, and 4) procedures for use of the parameters in the groundwater exposure assessment. The draft guidance was revised after feedback from stakeholders and testing of the guidance was performed against real data sets by an independent consultancy. The Chemicals Regulation Directorate submitted the revised document to the European Food Safety Authority (EFSA) for scrutiny. This article gives an overview of the draft guidance and explains the reasoning behind the recommendations made.

Reanalysis of experiments to quantify irreversibility of pesticide sorption-desorption in soil.

Previously published research used an isotope-exchange technique to measure irreversibility of pesticide sorption-desorption in soil. Results indicated significant irreversibility (6-51%) in sorption in five pesticide-soil systems measured over 72 h. Here, we propose a three-site model to reanalyze the experimental data. The model adds a slow but reversible binding on nonequilibrium sorption sites in addition to instantaneously reversible sites and irreversible sites. The model was able to match experimental data very closely, but only if irreversible sorption was assumed to be absent. Observed asymmetry in the binding of (12)C- and (14)C-pesticide was explained on the basis of nonattainment of sorption equilibrium over the study period. Results suggest that irreversible sorption may be less significant than previously considered with important implications for understanding the fate of pesticides applied to soil.

Pesticide transport via sub-surface drains in Europe.

Transport of pesticides from point of application via sub-surface drains can contribute significantly to contamination of surface waters. Results of 23 field drainage experiments undertaken at sites across Europe were collated and analysed by residual maximum likelihood. Both maximum concentration of pesticide in drainflow (n = 167) and seasonal loss of pesticide to drains (n = 97) were significantly related to strength of pesticide sorption to soil, half-life of the pesticide in soil, the interval between application and first drainflow and the clay content of the soil. The statistical models accounted for 71% of the variability in both maximum concentration and seasonal load. Next, the dataset was used to evaluate the current methodology for assessment of aquatic exposure used in pesticide registration in Europe. Simulations for seven compounds with contrasting properties showed a good correspondence with field measurements. Finally, the review examines management approaches to reduce pesticide transport via sub-surface drains. Despite a large amount of work in this area, there are few dependable mitigation options other than to change application rate or timing or to restrict use of a compound in the most vulnerable situations.

How does crop type influence risk from pesticides to the aquatic environment?

National-level risk mapping was undertaken to identify specific situations within England with the greatest potential for impacts on aquatic biodiversity from normal agricultural use of pesticides. Calculations of exposure via spray drift and drainflow were differentiated by landscape type, region, and crop and then compared with toxicity to the indicator organisms Daphnia magna and algae. The approach incorporated regional-level information regarding pesticide usage derived from farm visits. Risk was calculated for individual water bodies and then aggregated and mapped for each of 5,760 individual catchments ranging in area up to 248 km2. Type of crop adjacent to water was the major driver for risk, and orchards were identified as the crop associated with the greatest potential risk to the aquatic environment. Crops such as cereals, oilseeds, and potatoes are more widely grown in England but have potential risk an order of magnitude smaller than that for orchards. Several of the pesticides that contribute most to risk have been withdrawn from use since collection of the most recent usage data. Driven by crop distribution, surface waters adjacent to orchards in the midwest and southeast of England are predicted to be most at risk of ecological impacts from agricultural pesticide use. This information can be used in targeting monitoring campaigns designed to protect the aquatic environment.

Lysimeter experiment to investigate the potential influence of diffusion-limited sorption on pesticide availability for leaching.

Pesticide leaching from soil has been shown to decrease with increasing time from application to irrigation. It is hypothesized that the availability of compounds for leaching decreases due to diffusion and sorption inside soil aggregates. Previous work showed that pesticide sorption inside soil aggregates increases significantly during the first days after application. The study presented here tested if diffusion into aggregates could explain the leaching of four aged pesticides from manually irrigated soil cores. Azoxystrobin, chlorotoluron, cyanazine, and bentazone were applied to 30 undisturbed cores (25 cm long, 23.7 cm diameter) from a clay loam soil. The soil cores were irrigated 1, 3, 7, 14, and 28 days after application. Leachate was collected and analyzed. The amount of pesticide found in leachate decreased rapidly with time from application. Pesticide losses in leachate declined 2.5-27 times faster than total residues in soil. The decline was 4-5 times faster for the more strongly sorbed pesticides (azoxystrobin, chlorotoluron, and cyanazine) than for bentazone. In previous work, we derived a model to describe sorption and diffusion of the pesticides in small aggregates from the same soil. The diffusion model was used here to describe sorption inside the large aggregates in the soil cores and extended to describe pesticide leaching by interaggregate flow. The model showed a significant decline in leaching with time from application, which supports the theory that diffusion-limited sorption in aggregates influences the availability for pesticide leaching, although it does not exclude alternative explanations for this decline. The model well described the decline in leaching for three out of four pesticides. The interaggregate transport model could, however, not account for the amount of preferential flow in the cores and underestimated the leaching of bentazone.

Competitive sorption and diffusion of chromate and sulphate in a flow system with goethite in gel beads.

Column experiments and model simulations were employed to evaluate the processes involved in multicomponent solute transport in a system with heterogeneous flow. Column experiments were performed with goethite embedded in polyacrylamide gel beads. The gel forms an immobile water region that can be accessed by diffusion. A two-region transport model with diffusion into spheres was combined with a surface complexation model to predict reactive transport in the goethite-gel bead system. Chromate and sulphate breakthrough curves were measured in a set of transport experiments, along with corresponding changes in the pH of the effluent. Sorption and transport of sulphate and chromate in separate columns were predicted from independently measured sorption parameters. The model overestimated the pH changes in the effluent, possibly because of proton buffering by the polyacrylamide gel. The effect of competitive sorption on transport was examined in experiments with both anions present. The model predicted the effect of competition very well in a system initially equilibrated with sulphate, followed by infiltration with chromate. However, when sulphate was infiltrated after equilibration with chromate, chromate desorption and sulphate adsorption were clearly overestimated by the transport model. The exchange between the more strongly bound chromate and the sulphate added subsequently may be too slow to cause a substantial chromate peak in the effluent. This suggests that the local equilibrium assumption was not applicable in this case.

Pesticide sorption and desorption by lignin described by an intraparticle diffusion model.

Lignin was used as a model compound for soil organic matter to gain insight into the mechanisms that control the kinetics of pesticide sorption and desorption. Hydrolytic lignin was immobilized in a matrix of alginate gel, and sorption-desorption experiments were undertaken with isoproturon. Sorption increased with time and was close to equilibrium after 14 days. Desorption was measured after sorption for different time intervals and for a number of successive desorption steps of different lengths. The results showed strong differences between the sorption and desorption isotherms. The ratio of sorbed to dissolved pesticide approached and even exceeded the equilibrium ratio, depending on the number of desorption steps and the length of each equilibration period. A numerical diffusion model was developed to describe radial diffusion into the lignin particles in combination with Freundlich sorption inside the particles. Key model parameters were adjusted to fit the sorption data, and the same parameters were then used to predict stepwise desorption. Desorption was well described by the model, which suggests that sorption and desorption were driven by the same mechanism and occurred at the same rate. The observed difference between the sorption and desorption isotherms could be fully explained by the nonattainment of equilibrium due to slow diffusion into and out of the lignin particles.

Pesticide sorption and diffusion in natural clay loam aggregates.

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.

Evaluation of simplifying assumptions on pesticide degradation in soil.

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.

Sorption kinetics of strontium in porous hydrous ferric oxide aggregates I. The Donnan diffusion model.

Sorption of ions by hydrous ferric oxide (HFO) often shows a fast initial sorption reaction followed by a much slower sorption process. The second step is diffusion-controlled and can continue for days or months before equilibrium is reached. In this paper, we demonstrate that the diffusion rate may be explained by electrostatic interactions. The internal and external surfaces of HFO are generally positively charged and therefore repel cations. This can result in extremely low cation concentrations in pores, and therefore a significant reduction in pore diffusion rate. The theory is demonstrated here for sorption of Sr(2+) in HFO aggregates. The ion concentrations in the pore space are calculated using a Donnan model and diffusion is calculated from the Donnan concentration and potential gradients. This diffusion model is compared with nonelectrostatic pore diffusion, which does not take electrostatic interactions into account. The Donnan model predicts very low concentrations of Sr(2+) in the pores and diffusion rates that are up to 8000 times lower than predicted with a nonelectrostatic model.

Sorption kinetics of strontium in porous hydrous ferric oxide aggregates II. Comparison of experimental results and model predictions.

In a previous paper, we introduced the Donnan diffusion model to describe cation diffusion into microporous solids with variably charged surfaces, such as hydrous ferric oxides (HFO). Here, we present experiments investigating slow diffusion and sorption of strontium by HFO aggregates with well-characterized porosity. Adsorption of protons and strontium at the HFO surface was evaluated by acid-base titration and batch adsorption experiments with dispersed HFO. The experimental data were fitted with a 1-pK basic Stern model including surface ion pair formation of Na(+) and NO(3)(-) and charge distribution for Sr surface complexes. Sorption-diffusion experiments were conducted in flow-through columns at controlled flow rates and at two different pH values, pH 4 and 7. Wet HFO aggregates, which were synthesized using a freezing and thawing method, were packed into chromatographic columns, pre-equilibrated to reach a constant pH, and then Sr breakthrough curves for adsorption and desorption of Sr were recorded. Strong retardation of Sr indicated that diffusion was sufficiently fast in a fraction of pores, so that sorption sites in these pores were rapidly accessible. Based on the analysis of NaNO(3) breakthrough curves, this rapidly accessible pore fraction was estimated to be 37% of the total aggregate pore volume at pH 4.0 and 72% at pH 7.0, respectively. Taking this into account, the Donnan diffusion model gave a good description of the experimental Sr breakthrough curves. Cation exclusion was correctly predicted at pH 4.0. At pH 7, the strong tailing of Sr breakthrough curves due to Sr diffusion into the smallest pores was very well simulated. The Donnan diffusion model proved adequate for pore sizes between approximately 2 and 5 nm, depending on pH and ionic strength. This category of pores was dominant in the HFO aggregates used in this work.

Determination of time-dependent partition coefficients for several pesticides using diffusion theory.

Diffusion-retarded partitioning of pesticides with aggregated soils results in a time-dependent partition coefficient (Kd') which is different at equilibrium from the partition coefficient derived from conventional 24-h batch studies (Kd) measured on dispersed soil. An experiment was undertaken to determine the importance of Kd' for the prediction of pesticide concentrations in solutions bathing artificial soil aggregates and to determine whether diffusion theory could accurately predict the concentrations. Two clay soils were mixed with polyacrylamide to create artificial aggregates of 0.8, 1.4 and 1.7 cm diameter when dry. After saturation, the aggregates were immersed in solutions containing isoproturon or a mixture of isoproturon, chlorotoluron and triasulfuron. The decline with time of the pesticide concentrations in the bathing solution was monitored and the results were compared with predictions from a diffusion-based model. The effective diffusion coefficients of the compounds were obtained by either fitting the non-linear diffusion model to the data (D(ef)) or by independent calculations based on the properties of the compounds and of the aggregates (D(ec)). The diffusion model was able to predict the temporal variation in pesticide concentrations in the bathing solution reasonably well whether D(ef) or D(ec) values were used. However, equilibrium concentrations in solution were sometimes overestimated due to increased sorption with time at the particle scale. Overall, the ratio between D(ef) and D(ec) ranged from 0.23 to 0.95 which was a reasonable variation when compared to the range of aggregate sizes used in the experiments and of the Kd values of the compounds.

Influence of kinetic sorption and diffusion on pesticide movement through aggregated soils.

Laboratory studies were carried out to investigate solute leaching at different times from application in relation to temperature and initial soil moisture. Aggregates of a heavy clay soil were treated with a non-interactive solute (bromide) and the herbicides chlorotoluron, isoproturon and triasulfuron. The soil was incubated at 90% field capacity and either 5 or 15 degrees C. The influence of application to initially dry and initially wet aggregates on the behaviour of isoproturon was also investigated. At intervals, samples were either leached in small columns, centrifuged to characterise the fraction of chemical available in pore water under natural moisture conditions or extracted with organic solvents to assess total residues in soil. Bromide concentrations in leachate and in pore water extracted by centrifugation were constant with time. In contrast, availability for leaching and concentration in pore water of the herbicides decreased with increasing time from application in soil incubated at 15 degrees C. The effect of residence time was much smaller at 5 than at 15 degrees C. At the higher temperature, pesticide concentrations in leachate and pore water declined faster than would be expected from degradation alone, probably due to slow diffusion of the pesticides into soil aggregates where they are less available for leaching and/or slow sorption-desorption. The faster decline in availability for leaching at 15 than at 5 degrees C was attributed to faster degradation of the readily available fraction. There was no significant influence of initial soil moisture on either the leaching behaviour of isoproturon or its availability in soil water.