Influence of ageing of residues on the availability of herbicides for leaching

Losses by leaching of chlorotoluron, isoproturon and triasulfuron from small intact columns of a structured clay loam and an unstructured sandy loam soil were measured in five separate field experiments. In general, losses of all three herbicides were greater from the clay loam than from the sandy loam soil and the order between herbicides was always triasulfuron > isoproturon > chlorotoluron. Differences between experiments were also consistent for every soil/herbicide combination. There was no relationship between total loss and either total rainfall or cumulative leachate volume. When weighting factors were applied to the rainfall data to make early rainfall more important than later rainfall, there were significant positive relationships between cumulative weighted rainfall and total losses. Also, there were significant negative correlations between total losses and the delay to accumulation of 25 mm rainfall (equivalent to one pore volume of available water) in the different experiments. In laboratory incubations, there was a more rapid decline in aqueous (0.01 M calcium chloride) extractable residues than in total solvent extractable residues indicating increasing sorption with residence time. However, the rate of change in water extractable residues could not completely explain the decrease in leachability with ageing of residues in the field. Short-term sorption studies with aggregates of the two soils indicated slower sorption by those of the clay loam than by those of the sandy loam suggesting that diffusion into and out of aggregates may affect availability for leaching in the more structured soil. Small scale leaching studies with aggregates of the soils also demonstrated reductions in availability for leaching as residence time in soil was increased, which could not be explained by degradation. These results therefore indicate that time-dependent sorption processes are important in controlling pesticide movement in soils, although the data do not give a mechanistic explanation of the changes in leaching with ageing of residues.     

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.     

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.     

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.     

Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils

The Gharb region in Morocco is an important agricultural zone where soils receive pesticide treatments and organic amendments to increase yields. The groundwater aquifer in the Gharb region is relatively shallow and thus vulnerable. The objective of this work was to study the influence of organic amendments on diuron, cyhalofop-butyl and procymidone leaching through undisturbed soil columns. Two soils were sampled from the Gharb region, a Dehs (sandy soil) and a R’mel (loamy clay soil). Following elution (124.5 mm), the amount of pesticide residues in the leachates of the sandy soil (0.06–0.21 %) was lower than in those of the loamy clay soil (0.20–0.36 %), which was probably due to preferential flow through the loamy clay soil. The amount of procymidone leached through the amended soil columns was greater than the control for the sandy soil only. The organic amendments did not significantly influence diuron and cyhalofop-butyl leaching in either of the soils. The application of organic amendments affected the amounts of dissolved organic matter (DOM) eluted and thus pesticide leaching as a function of soil-type. Nevertheless, in some case, the formation of pesticide-DOM complexes appeared to promote pesticide leaching, thus increasing groundwater contamination risks.     

Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils

The Gharb region in Morocco is an important agricultural zone where soils receive pesticide treatments and organic amendments to increase yields. The groundwater aquifer in the Gharb region is relatively shallow and thus vulnerable. The objective of this work was to study the influence of organic amendments on diuron, cyhalofop-butyl and procymidone leaching through undisturbed soil columns. Two soils were sampled from the Gharb region, a Dehs (sandy soil) and a R'mel (loamy clay soil). Following elution (124.5 mm), the amount of pesticide residues in the leachates of the sandy soil (0.06-0.21 %) was lower than in those of the loamy clay soil (0.20-0.36 %), which was probably due to preferential flow through the loamy clay soil. The amount of procymidone leached through the amended soil columns was greater than the control for the sandy soil only. The organic amendments did not significantly influence diuron and cyhalofop-butyl leaching in either of the soils. The application of organic amendments affected the amounts of dissolved organic matter (DOM) eluted and thus pesticide leaching as a function of soil-type. Nevertheless, in some case, the formation of pesticide-DOM complexes appeared to promote pesticide leaching, thus increasing groundwater contamination risks.     

Penetration of herbicides to groundwater in an unconfined chalk aquifer following normal soil applications

The persistence and penetration of the herbicides isoproturon and chlorotoluron in an unconfined chalk aquifer has been monitored over a 4-year period through soil sampling, shallow coring and groundwater monitoring. Chlorotoluron was applied on plots as a marker compound, having never been used previously on that, or surrounding fields. The fieldsite had a 5 degree slope with soil depths of 0.5 to 1.5 m and a water table between 20 and 5 m from the soil surface. Where the water table was deepest (9-20 m below surface (mbs)) little or no positive herbicide detections were made. However, where the water table was at only 4-5 mbs, a regular pesticide signal of around 0.1 microg/l for isoproturon and chlorotoluron could be distinguished. Over the winter recharge period automatic borehole samplers revealed a series of short-lived peaks of isoproturon and chlorotoluron reaching up to 0.8 microg/l. This is consistent with a preferential flow mechanism operating at this particular part of the field. Such peaks were occurring over 2 years after the last application of these compounds. Shallow coring failed to uncover any significant pesticide pulse moving through the deep unsaturated zone matrix at the fieldsite.     

Sorption, degradation, and leaching of tebuthiuron and diuron in soil columns

A study in small outdoor lysimeters was carried out to determine the leaching of the herbicides tebuthiuron and diuron in different soil types, using undisturbed soil columns. Soil sorption and degradation for both herbicides were also studied in the laboratory. The multi-layered AF (Attenuation Factor) model was evaluated for predicting the herbicides leaching in undisturbed soil columns. Tebuthiuron leached in greater amounts than diuron in both soils. Sorption was well represented by linear and Freundlich equations, however parameters from the linear equations were used in the AF model. In general, both herbicides presented very low sorption, with diuron presenting lower values of sorption coefficient than tebuthiuron in the two soils. Chromatographic data indicated rapid late degradation of diuron and tebuthiuron in both soil types at two different depths. Simple exponential equation was not able to represent degradation, thus a bi-exponential equation was used, and some model adjusting was needed. Average measured amounts of each herbicide were compared with amounts predicted by the multi-layered-soil AF model. The AF model was able to predict leaching amounts in the sandy soil, especially for diuron, however it did not perform well in the clayey soil.     

Assessment of phenylurea herbicides sorption on various Mediterranean soils affected by irrigation with wastewater

The retention values of two herbicides, chlorotoluron and isoproturon, in five Mediterranean soils were assessed by two different approaches, a dynamic method, using a batch technique (BT) and a static method, using a soil saturated paste (SP). The SP method led in all cases to lower herbicide sorption when compared with BT, although pesticide distribution constants from both methods were linearly related for the set of used soils (R² ? 0.99) showing that both methods similarly reflected the behaviour of the different soils. Low-quality water, evaluated by employing recycled urban wastewater, did not modify herbicide sorption when compared with high quality water, in any soil and with any method.     

Limitations on the role of incorporated organic matter in reducing pesticide leaching.

The use of organic amendments has been suggested as a method of controlling pesticide leaching through soils. The enarenados soils of the intensive horticulture of the Almeria province of southern Spain contain buried organic matter horizons above a soil layer amended with clay. This region is ideal for understanding the potential for and limitations of organic amendments in preventing pesticide pollution. This study measured the sorption and degradation potential of carbofuran in this soil system and the hydrological behaviour of the soil horizons. The sorption of carbofuran was controlled by the organic carbon content, the degradation was strongly pH-dependent and the acidic organic layer protected the sorbed carbofuran against degradation. Hydrologically, the soil system is dominated by ponding above an amended clay layer and by the presence of macropores that can transport water through this clay. A simple model is proposed on this basis and shows that although high levels of dissolved organic carbon can be released by buried organic horizons, the major control on re-release of sorbed pesticide is the potential for sorption hysteresis in this organic layer. A comparison of sorption and degradation data for carbamate insecticides used in the region with groundwater observations for these compounds shows that no amount of incorporated organic would protect against pollution from highly water-soluble compounds.     

Effect of grass cover on water and pesticide transport through undisturbed soil columns, comparison with field study (Morcille watershed, Beaujolais)

The purpose of this work is to assess the effectiveness of two grass covers (buffer zone and grass-covered inter-row), to reduce pesticide leaching, and subsequently to preserve groundwater quality. Lower amounts of pesticides leached through grass-cover soil columns (2.7-24.3% of the initial amount) than the bare soil columns (8.0-55.1%), in correspondence with their sorption coefficients. Diuron was recovered in higher amounts in leachates (8.9-32.2%) than tebuconazole (2.7-12.9%), in agreement with their sorption coefficients. However, despite having a sorption coefficient similar to that of diuron, more procymidone was recovered in the leachates (10.2-55.1%), probably due to its facilitated transport by dissolved organic matter. Thus even in this very permeable soil, higher organic matter contents associated with grass-cover reduce the amount of pesticide leaching and limit the risk of groundwater contamination by the pesticides. The results of diuron and tebuconazole transfer through undisturbed buffer zone soil columns are in agreement with field observations on the buffer zone.     

Multi-process herbicide transport in structured soil columns: experiments and model analysis

Model predictions of pesticide transport in structured soils are complicated by multiple processes acting concurrently. In this study, the hydraulic, physical, and chemical nonequilibrium (HNE, PNE, and CNE, respectively) processes governing herbicide transport under variably saturated flow conditions were studied. Bromide (Br-), isoproturon (IPU, 3-(4-isoprpylphenyl)-1,1-dimethylurea) and terbuthylazine (TER, N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine) were applied to two soil columns. An aggregated Ap soil column and a macroporous, aggregated Ah soil column were irrigated at a rate of 1 cm h(-1) for 3 h. Two more irrigations at the same rate and duration followed in weekly intervals. Nonlinear (Freundlich) equilibrium and two-site kinetic sorption parameters were determined for IPU and TER using batch experiments. The observed water flow and Br- transport were inversely simulated using mobile-immobile (MIM), dual-permeability (DPM), and combined triple-porosity (DP-MIM) numerical models implemented in HYDRUS-1D, with improving correspondence between empirical data and model results. Using the estimated HNE and PNE parameters together with batch-test derived equilibrium sorption parameters, the preferential breakthrough of the weakly adsorbed IPU in the Ah soil could be reasonably well predicted with the DPM approach, whereas leaching of the strongly adsorbed TER was predicted less well. The transport of IPU and TER through the aggregated Ap soil could be described consistently only when HNE, PNE, and CNE were simultaneously accounted for using the DPM. Inverse parameter estimation suggested that two-site kinetic sorption in inter-aggregate flow paths was reduced as compared to within aggregates, and that large values for the first-order degradation rate were an artifact caused by irreversible sorption. Overall, our results should be helpful to enhance the understanding and modeling of multi-process pesticide transport through structured soils during variably saturated water flow.     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

Determination of solid-liquid partition coefficients (Kd) for the herbicides isoproturon and trifluralin in five UK agricultural soils

Isoproturon and trifluralin are herbicides of contrasting chemical characters and modes of action. Standard batch sorption procedures were carried out to investigate the individual sorption behaviour of 14C-isoproturon and 14C-trifluralin in five agricultural soils (1.8-4.2% OC), and the soil solid-liquid partition coefficients (Kd values) were determined. Trifluralin exhibited strong partitioning to the soil solid phase (Kd range 106-294) and low desorption potential, thus should not pose a threat to sensitive waters via leaching, although particle erosion and preferential flow pathways may facilitate transport. For isoproturon, soil adsorption was low (Kd range 1.96-5.75) and desorption was high, suggesting a high leaching potential, consistent with isoproturon being the most frequently found pesticide in UK surface waters. Soil partitioning was directly related to soil organic carbon (OC) content. Accumulation isotherms were modelled using a dual-phase adsorption model to estimate adsorption and desorption rate coefficients. Associations between herbicides and soil humic substances were also shown using gel filtration chromatography.     

Influence of a heavy rainfall event on the leaching of [14C]isoproturon and its degradation products in outdoor lysimeters

In four different agricultural soils the long-term leaching behaviour of [14C]isoproturon was studied in outdoor lysimeters (2 m length, 1 m2 surface area). The herbicide was applied in spring 1997 and spring 2001. At the end of the first 4-year-investigation period between 0.13% and 0.31% of the applied radioactivity was leached. Isoproturon or known metabolites could not be detected in the leachate. However, shortly after the second application isoproturon and its degradation products 2-hydroxy-isoproturon and monodemethyl-isoproturon were leached via preferential flow in one of the lysimeters (Mollic gleysol) in concentrations of 4.5 microg L-1, 3.1 microg L-1 and 0.9 microg L-1, respectively, thus considerably exceeding the EU threshold limit of 0.1 microg L-1 for ground and drinking water. The results indicate that in soils where mass flow transfer dominates, leaching of isoproturon to groundwater is of low probability whereas in highly structured soils which have the tendency to form macropores, isoproturon can be transported via preferential flow to the groundwater.     

Effect of charcoal amendment on adsorption, leaching and degradation of isoproturon in soils

The effects of charcoal amendment on adsorption, leaching and degradation of the herbicide isoproturon in soils were studied under laboratory conditions. The adsorption data all fitted well with the Freundlich empirical equation. It was found that the adsorption of isoproturon in soils increased with the rate of charcoal amended (correlation coefficient r=0.957**, P<0.01). The amount of isoproturon in leachate decreased with the increase of the amount of charcoal addition to soil column, while the retention of isoproturon in soils increased with an increase in the charcoal content of soil samples. Biodegradation was still the most significant mechanism for isoproturon dissipation from soil. Charcoal amendment greatly reduced the biodegradation of isoproturon in soils. The half-lives of isoproturon degradation (DT(50)) in soils greatly extended when the rate of added charcoal increased from 0 to 50 g kg(-1) (for Paddy soil, DT(50) values increased from 54.6 to 71.4 days; for Alfisol, DT(50) from 16.0 to 136 days; and for Vertisol, DT(50) from 15.2 to 107 days). The degradation rate of isoproturon in soils was significantly negatively correlated with the amount of added charcoal. This research suggests that charcoal amendment may be an effective management practice for reducing pesticide leaching and enhancing its persistence in soils.     

Fate of napropamide herbicide in selected Malaysian soils

This study was carried out to determine the sorption-desorption, degradation and leaching of napropamide in selected Malaysian soils. The sorption capacities of the selected Malaysian soils for napropamide were the following in descending order: Linau > Teringkap > Gunung Berinchang > Jambu > Rudua > Baging soil. The results indicate that napropamide degradation decreased with increasing soil sorption capacity. Napropamide was leached out earlier in the Baging soil than the other soils. Overall, the application of napropamide in the selected Malaysian soils would not pose a threat to the environment except in soil with low organic matter and clay content and high hydraulic conductivity, such as the Baging soil.     

Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil

Laboratory studies were conducted to characterise four different antibiotic compounds with regard to sorption and mobility in various soil types. Distribution coefficients (Kd values) determined by a batch equilibrium method varied between 0.5 and 0.7 for metronidazole, 0.7 and 1.7 for olaquindox and 8 and 128 for tylosin. Tylosin sorption seems to correlate positively with the soil clay content. No other significant interactions between soil characteristics and sorption were observed. Oxytetracycline was particularly strongly sorbed in all soils investigated, with Kd values between 417 in sand soil and 1026 in sandy loam, and no significant desorption was observed. Soil column leaching experiments indicated large differences in the mobility of the four antibiotic substances, corresponding to their respective sorption capabilities. For the weakly adsorbed substances metronidazole and olaquindox the total amounts added were recovered in the leachate of both sandy loam and sand soils. For the strongly adsorbed oxytetracyline and tylosin nothing was detected in the leachate of any of the soil types, indicating a much lower mobility. Results from defractionation and extraction of the columns (30 cm length) showed that 60-80% of the tylosin added had been leached to a depth of 5 cm in the sandy loam soil and 25 cm in the sand soil.     

Movement of metolachlor and terbuthylazine in core and packed soil columns

Movement of metolachlor and terbuthylazine including a bromide tracer was studied in core and packed soil columns in PVC pipes (80 mm diameter, 15 mm depth) with two German soil types viz: silt loam and loamy silt. The breakthrough curves (BTCs) for bromide indicated some preferential flow of water both under conventional tillage (CN) and no-till (NT) simulation with silt loam soil. The herbicides leached to a greater extent in NT columns than in CN columns. Leaching was higher in loamy silt soil than in silt loam soil under CN conditions. This result is in agreement with the higher sorption capacity of silt loam having higher organic carbon compared to loamy silt having low organic carbon. Adsorption strength of the herbicides did not affect their breakthrough time, but was reflected in the slope and maximum height of the BTCs. The BTCs showed the expected inverse relationship between leaching and adsorption with greater mobility of the weakly-sorbed metolachlor than the more strongly sorbed terbuthylazine. Maximum amounts of the applied herbicides were recovered from the top soil layer in intact columns. Metolachlor was more mobile in packed columns than in core columns.