The effect of initial concentration of carbofuran on the development and stability of its enhanced biodegradation in top‐soil and sub‐soil

Carbofuran was incubated in top‐soil and sub‐soil samples from a pesticide‐free site at a range of initial concentrations from 0.1 to 10 mg kg⁻¹. Amounts of the incubated soils were removed at intervals over the subsequent 12 months, and the rate of degradation of a second carbofuran dose at 10 mg kg⁻¹ was assessed. An applied concentration as low as 0.1 mg kg⁻¹ to top‐soil resulted in more rapid degradation of the fresh addition of carbofuran for at least 12 months. The degree of enhancement was generally more pronounced with the higher initial concentrations. When the same study was conducted in sub‐soil samples from the same site, an initial dose of carbofuran at 0.1 mg kg⁻¹ resulted in only small increases in rates of degradation of a second carbofuran dose. However, degradation rates in the sub‐soil samples were, in many instances, considerably greater than in the corresponding top‐soil samples, irrespective of pre‐treatment concentration or pre‐incubation period. Initial doses of 0.5 mg kg⁻¹ and higher applied to sub‐soil successfully activated the sub‐soil microflora. Application of the VARLEACH model to simulate carbofuran movement through the soil profile indicated that approximately 0.01 mg kg⁻¹ of carbofuran may reach a depth of 70 cm 400 days after a standard field application. The results therefore imply that adaptation of the sub‐soil microflora (c 1 m depth) by normal field rate applications of carbofuran is unlikely to occur. In experiments to investigate this in soils exposed to carbofuran in the field, there was no apparent relationship between top‐soil exposure and degradation rates in the corresponding sub‐soils. The results further confirmed that some sub‐soil samples have an inherent capacity for rapid biodegradation of carbofuran. The high levels of variability observed between replicates in some of the sub‐soil samples were attributed to the uneven distribution of a low population of carbofuran‐degrading micro‐organisms in sub‐surface soil. There was no apparent relationship between soil microbial biomass and degradation rates within or between top‐soil and sub‐soil samples. © 2001 Society of Chemical Industry     

Quantifying interactions between compound properties and macropore flow effects on pesticide leaching

The objective of this study was to investigate the interactions between compound properties and macropore flow effects on pesticide leaching. To this end, the dual‐porosity MACRO model was used to simulate leaching of 60 hypothetical compounds with widely differing sorption and degradation characteristics using a pre‐calibrated scenario from Lanna, south‐west Sweden, representing a structured clay soil. The model predicts that, in the worst case, macropore flow increases leaching by more than four orders of magnitude for moderately to strongly sorbed compounds with relatively short half‐lives. However, it was also notable that leaching of some very mobile compounds is actually reduced by macropore flow. For pesticides leaching between 0.0001 and 10% of the applied dose (without macropore flow), the impact of pesticide properties on leaching is markedly reduced. This suggests that reductions in applied dose become a relatively more attractive and effective means of decreasing leaching from structured soils. © 2000 Society of Chemical Industry     

Persistence of pyrazosulfuron in rice-field and laboratory soil under Indian tropical conditions

BACKGROUND: Pyrazosulfuron ethyl, a new rice herbicide belonging to the sulfonylurea group, has recently been registered in India for weed control in rice crops. Many field experiments revealed the bioefficacy of this herbicide; however, no information is available on the persistence of this herbicide in paddy soil under Indian tropical conditions. Therefore, a field experiment was undertaken to investigate the fate of pyrazosulfuron ethyl in soil and water of rice fields. Persistence studies were also carried out under laboratory conditions in sterile and non‐sterile soil to evaluate the microbial contribution to degradation. RESULTS: High‐performance liquid chromatography (HPLC) of pyrazosulfuron ethyl gave a single sharp peak at 3.41 min. The instrument detection limit (IDL) for pyrazosulfuron ethyl by HPLC was 0.1 µg mL^?1, with a sensitivity of 2 ng. The estimated method detection limit (EMDL) was 0.001 µg mL^?1 and 0.002 µg g^?1 for water and soil respectively. Two applications at an interval of 10 days gave good weed control. The herbicide residues dissipated faster in water than in soil. In the present study, with a field‐soil pH of 8.2 and an organic matter content of 0.5%, the pyrazosulfuron ethyl residues dissipated with a half‐life of 5.4 and 0.9 days in soil and water respectively. Dissipation followed first‐order kinetics. Under laboratory conditions, degradation of pyrazosulfuron ethyl was faster in non‐sterile soil (t_1/2 = 9.7 days) than in sterile soil (t_1/2 = 16.9 days). CONCLUSION: Pyrazosulfuron ethyl is a short‐lived molecule, and it dissipated rapidly in field soil and water. The faster degradation of pyrazosulfuron in non‐sterile soil than in sterile soil indicated microbial degradation of this herbicide. Copyright © 2012 Society of Chemical Industry     

The Validation of Pesticide Leaching Models

The validation of pesticide leaching models presents particular problems where the number of model predictions is far in excess of the observed data. Normally, however, there are more frequent field observations for other parameters (notably the site hydrology) than for pesticide concentrations in either water or soil. A five-stage validation procedure which takes advantage of the most frequently available observations and which tests each of the components of the model in a cumulative way, is thus advocated: Stage 1: Parameterisation of the model using only independently measured parameters. Stage 2: Hydrological validation: the validation of the predictions of water movement and water content of the soil. Stage 3: Solute movement validation: where field data are available for solutes other than pesticide, the model should first be validated for them, especially if they are more abundant than the pesticide observations. Conserved solutes such as chloride or bromide are preferred, although nitrate may be used for short periods. Stage 4: Pesticide fate in the soil: models should use parameters of pesticide fate derived from independent studies. Stage 5: Pesticide leaching: only in the last stage are the relatively small number of pesticide observations compared with the model predictions with respect to patterns and orders of magnitude of occurrence. With this scheme, the results of each stage are carried forward to the next, and confidence in the model is built with each stage. This is illustrated using the CRACK-P model and hydrological, nitrate and pesticide data from the Brimstone Farm Experiment Oxfordshire, UK.     

Application of the pesticide transport assessment model to a field study in a humic sandy soil in Vredepeel,The Netherlands

The Pesticide Transport Assessment model (PESTRAS) is a process-oriented model to simulate the fate and movement of water and pesticides in a cropped field soil. The model was evaluated using field data for bromide, ethoprophos and bentazone, collected from a field experiment in a humic sandy soil near Vredepeel, the Netherlands. Model predictions were generally within the 95% confidence intervals of the observations when site-specific model inputs were used. If generic parameter values were used, the model predictions sometimes deviated strongly from the observed data. This was especially true for pesticide degradation properties. The bromide simulations showed that preferential flow was not an important process for this field soil. A significant fraction of the applied ethoprophos disappeared by surface volatilization. The downward movement of this pesticide was slightly overestimated, due to not considering sorption kinetics. The depth-dependence of pesticide transformation was atypical: an important fraction of the applied bentazone was transformed under micro-aerobic to anaerobic conditions in the subsoil. © 1998 SCI     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

Testing MACRO (version 5.1) for pesticide leaching in a Dutch clay soil

Testing of pesticide leaching models against comprehensive field-scale measurements is necessary to increase confidence in their predictive ability when used as regulatory tools. Version 5.1 of the MACRO model was tested against measurements of water flow and the behaviour of bromide, bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide] and imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] in a cracked clay soil. In keeping with EU (FOCUS) procedures, the model was first calibrated against the measured moisture profiles and bromide concentrations in soil and in drain water. Uncalibrated pesticide simulations based on laboratory measurements of sorption and degradation were then compared with field data on the leaching of bentazone and imidacloprid. Calibrated parameter values indicated that a high degree of physical non-equilibrium (i.e. strong macropore flow) was necessary to describe solute transport in this soil. Comparison of measured and simulated bentazone concentration profiles revealed that the bulk of the bentazone movement in this soil was underestimated by MACRO. Nevertheless, the model simulated the dynamics of the bentazone breakthrough in drain water rather well and, in particular, accurately simulated the timing and the concentration level of the early bentazone breakthrough in drain water. The imidacloprid concentration profiles and its persistence in soil were simulated well. Moreover, the timing of the early imidacloprid breakthrough in the drain water was simulated well, although the simulated concentrations were about 2-3 times larger than measured. Deep groundwater concentrations for all substances were underestimated by MACRO, although it simulated concentrations in the shallow groundwater reasonably well. It is concluded that, in the context of ecotoxicological risk assessments for surface water, MACRO can give reasonably good simulations of pesticide concentrations in water draining from cracking clay soils, but that prior calibration against hydrologic and tracer data is desirable to reduce uncertainty and improve accuracy.     

Simulation of movement of pesticides towards drains with a preferential flow version of PEARL

BACKGROUND: As part of the Dutch authorisation procedure for pesticides, an assessment of the effects on aquatic organisms in surface waters adjacent to agricultural fields is required. The peak concentration is considered to be the most important exposure endpoint for the ecotoxicological effect assessment. Macropore flow is an important driver for the peak concentration, so the leaching model PEARL was extended with a macropore module. The new model has two macropore domains: a bypass domain and an internal catchment domain. The model was tested against data from a field leaching study on a cracking clay soil in the Netherlands. RESULTS: Most parameters of the model could be obtained from site‐specific measurements, pedotransfer functions and general soil structural knowledge; only three macropore‐flow‐related parameters needed calibration. The flow‐related macropore parameters could not be calibrated without using the concentration in drain water. Sequential calibration strategies, in which firstly the water flow model and then the pesticide fate model are calibrated, may therefore be less suitable for preferential flow models. CONCLUSION: After calibration, PEARL could simulate well the observed rapid movement towards drains of two pesticides with contrasting sorption and degradation rate properties. The calibrated value for the fraction of the internal catchment domain was high (90%). This means that a large fraction of water entering the macropores infiltrates into the soil matrix, thus reducing the fraction of rapid flow. Copyright © 2011 Society of Chemical Industry     

Enhanced degradation in soil of tri-allate and other carbamate pesticides following application of tri-allate

Tri-allate degraded faster in soil from a site (T1) that had received 1·7 kg ha^?1 of tri-allate annually for 23 years than in soil from an adjacent site (TO) that had received no pesticide application. Soil from the untreated site, which had been removed to a glasshouse and treated three times per annum with tri-allate at 1·7 kg ha^?1 for 7 years (T2), also showed faster degradation. Soil previously treated with tri-allate showed an increased degradation rate for carbofuran and EPTC but not for aldicarb. A further experiment, 2 years after the last treatment with tri-allate, showed that the enhanced degradation effect was still present. Degradation rates were always in the order T1 > T2 > T0 for tri-allate, EPTC and carbofuran. Half-life for degradation was reduced for tri-allate and carbofuran by approximately 40% in the previously treated soils and for EPTC by approximately 80% when compared with the previously untreated soil.     

Influence of different field sites on pesticide movement into subsurface drains

Pesticide movement to subsurface drains was monitored in two typical crop production areas in Germany. Field trials were conducted on two subsurfacedrained soils, a silt loam and a poorly structured sandy soil, under different climatic conditions. Over a period of one year, the drainflow was measured and the drain water was analysed for all applied herbicides. Different leaching behaviour was observed at the two field sites. Following autumn application of pendimethalin and isoproturon to the Soester Börde soil, maximum concentrations of about 62 μg litre^?1 for isoproturon and 0.7 μg litre^?1 for pendimethalin were observed in drainflow from this silt loam. The early occurrence of both herbicides in the drain water only two days after application is consistent with fast flow through macropores. In contrast, on the subsurfacedrained sandy soil in Brandenburg, isoproturon did not reach the drains until two months after autumn application and was found at maximum concentrations of only 1.4 μg litre^?1; pendimethalin was not detected in the drain water. Pesticide movement after spring application seemed to be of minor importance. At both locations, spring application led to low concentrations of pesticides in the drainflow (pendimethalin < 0.01 μ litre^?1; metolachlor ? 0.05 μ litre^?1; chloridazon ? 0.15 μ litre^?1; metamitron ? 0.02 μg litre^?1; terbuthylazine ? 1.4 μ litre^?1).     

Residualwirkung von Chlortriazin-Herbiziden im Boden an drei rumänischen Standorten. I. Prognose der Persistenz von Simazin und Atrazin im Boden

Residual effects of chlorotriazine herbicides in soil at three Rumanian sites. I. Prediction of the persistence of simazine and atrazine Persistence of simazine and atrazine in the top 10 cm soil was measured at three sites in Rumania with variations in climate and soil conditions. Both herbicides were applied at 1 and 3 kg ai ha^?1 to uncropped plots and to plots cropped with maize (Zea mays L.). Rates of residue decline were independent of application rate and crop cover but varied between sites. The time for 50% loss of atrazine varied from 36 to 68 days and that of simazine from 48 to 70 days. Laboratory studies were made with atrazine to characterize degradation rates under standard conditions and to measure adsorption and leaching behaviour in the different soils. Weather records for the periods of the field experiments were used in conjunction with appropriate constants derived from the laboratory results, or from data in the literature, in a computer program to simulate persistence in the field. Results from the model were in reasonable agreement with the observed soil residues although there was a tendency to overestimate rates of loss on some occasions. The results suggest that the model of persistence was sufficiently accurate for practical purposes, and that its use could preclude the need for extensive analytical measurements of residues.     

Chlorpyrifos degradation in soil at termiticidal application rates

Chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate] is an organophosphorus insecticide applied to soil to control pests both in agricultural and in urban developments. Typical agricultural soil applications (0.56 to 5.6 kg ha^?1) result in initial soil surface residues of 0.3 to 32 μg g^?1. In contrast, termiticidal soil barrier treatments, a common urban use pattern, often result in initial soil residues of 1000 μg g^?1 or greater. The purpose of the present investigation was to understand better the degradation of chlorpyrifos in soil at termiticidal application rates and factors affecting its behaviour. Therefore, studies with [¹⁴C]chlorpyrifos were conducted under a variety of conditions in the laboratory. Initially, the degradation of chlorpyrifos at 1000 μg g^?1 initial concentration was examined in five different soils from termite-infested regions (Arizona, Florida, Hawaii, Texas) under standard conditions (25°C, field moisture capacity, darkness). Degradation half-lives in these soils ranged from 175 to 1576 days. The major metabolite formed in chlorpyrifos-treated soils was 3,5,6-trichloro-2-pyrid-inol, which represented up to 61% of applied radiocarbon after 13 months of incubation. Minor quantities of [¹⁴C]carbon dioxide (< 5%) and soil-bound residues (? 12%) were also present at that time. Subsequently, a factorial experiment examining chlorpyrifos degradation as affected by initial concentration (10, 100, 1000 μg g^?1), soil moisture (field moisture capacity, 1.5 MPa, air dry), and temperature 15, 25, 35°C) was conducted in the two soils which had displayed the most (Texas) and least (Florida) rapid rates of degradation. Chlorpyrifos degradation was significantly retarded at the 1000 μg g^?1 rate as compared to the 10 μg g^?1 rate. Temperature also had a dramatic effect on degradation rate, which approximately doubled with each 10°C increase in temperature. Results suggest that the extended (3–24 + years) termiticidal efficacy of chlorpyrifos observed in the field may be due both to the high initial concentrations employed (termite LC ₅₀ = 0.2– 2 μg g^?1) and the extended persistence which results from employment of these rates. The study also highlights the importance of investigating the behaviour of a pesticide under the diversity of agricultural and urban use scenarios in which it is employed.     

Behaviour of trifloxystrobin and tebuconazole on grapes under semi‐arid tropical climatic conditions

BACKGROUND: A mixture of trifloxystrobin and tebuconazole is excellent in controlling both powdery and downy mildew of grapes. The objective of the present work was to study the behaviour of trifloxystrobin and tebuconazole on grape berries and soil following treatment with Nativo 75 WG, a formulation containing both fungicides (trifloxystrobin 250 + tebuconazole 500 g kg^?1). This study was carried out for planned registration of this mixture for use on grapes in India. RESULTS: Initial residue deposits of trifloxystrobin and tebuconazole on grapes were below their maximum residue limit (MRL) of 0.5 and 2 mg kg^?1, respectively, when Nativo 75 WG was applied at the recommended dose of 175 g product ha^?1. The residues dissipated gradually to 0.02 and 0.05 mg kg^?1 by 30 days, and were below the quantifiable limit of 0.01 mg kg^?1 at the time of harvest (60 days after the last treatment). Trifloxystrobin and tebuconazole dissipated at a pre‐harvest interval (PHI) of 36 and 34 days, respectively, from the recommended treatment dose. The acid metabolite of trifloxystrobin, CGA 321 113, was not detected in grape berries at any point in time. Soil at harvest was free of any pesticide residues. CONCLUSION: Residue levels of both trifloxystrobin and tebuconazole were below MRLs when grapes were harvested 30 days after the last of four applications of 175 g product ha^?1 (trifloxystrobin 44 g AI ha^?1, tebuconazole 88 g AI ha^?1) under the semi‐arid tropical climatic conditions of India. Copyright © 2010 Society of Chemical Industry     

Field leaching of pesticides at five test sites in Hawaii: modeling flow and transport

BACKGROUND: Physically based tier‐II models may serve as possible alternatives to expensive field and laboratory leaching experiments required for pesticide approval and registration. The objective of this study was to predict pesticide fate and transport at five different sites in Hawaii using data from an earlier field leaching experiment and a one‐dimensional tier‐II model. As the predicted concentration profiles of pesticides did not provide close agreement with data, inverse modeling was used to obtain adequate reactive transport parameters. The estimated transport parameters of pesticides were also utilized in a tier‐I model, which is currently used by the state authorities to evaluate the relative leaching potential. RESULTS: Water flow in soil profiles was simulated by the tier‐II model with acceptable accuracy at all experimental sites. The observed concentration profiles and center of mass depths predicted by the tier‐II simulations based on optimized transport parameters provided better agreements than did the non‐optimized parameters. With optimized parameters, the tier‐I model also delivered results consistent with observed pesticide center of mass depths. CONCLUSION: Tier‐II numerical modeling helped to identify relevant transport processes in field leaching of pesticides. The process‐based modeling of water flow and pesticide transport, coupled with the inverse procedure, can contribute significantly to the evaluation of chemical leaching in Hawaii soils. Copyright © 2011 Society of Chemical Industry     

Herbicide leaching as affected by macropore flow and within-storm rainfall intensity variation: a RZWQM simulation

Within-event variability in rainfall intensity may affect pesticide leaching rates in soil, but most laboratory studies of pesticide leaching use a rainfall simulator operating at constant rainfall intensity, or cover the soil with ponded water. This is especially true in experiments where macropores are present--macroporous soils present experimental complexities enough without the added complexity of variable rainfall intensity. One way to get around this difficulty is to use a suitable pesticide transport model, calibrate it to describe accurately a fixed-intensity experiment, and then explore the affects of within-event rainfall intensity variation on pesticide leaching through macropores. We used the Root Zone Water Quality Model (RZWQM) to investigate the effect of variable rainfall intensity on alachlor and atrazine transport through macropores. Data were used from an experiment in which atrazine and alachlor were surface-applied to 30 x 30 x 30 cm undisturbed blocks of two macroporous silt loam soils from glacial till regions. One hour later the blocks were subjected to 30-mm simulated rain with constant intensity for 0.5 h. Percolate was collected and analyzed from 64 square cells at the base of the blocks. RZWQM was calibrated to describe accurately the atrazine and alachlor leaching data, and then a median Mid-west variable-intensity storm, in which the initial intensity was high, was simulated. The variable-intensity storm more than quadrupled alachlor losses and almost doubled atrazine losses in one soil over the constant-intensity storm of the same total depth. Also rainfall intensity may affect percolate-producing macroporosity and consequently pesticide transport through macropores. For example, under variable rainfall intensity RZWQM predicted the alachlor concentration to be 2.7 microg ml(-1) with an effective macroporosity of 2.2 E(-4) cm(3) cm(-3) and 1.4 microg ml(-1) with an effective macroporosity of 4.6 E(-4) cm(3) cm(-3). Percolate-producing macroporosity and herbicide leaching under different rainfall intensity patterns, however, are not well understood. Clearly, further investigation of rainfall intensity variation on pesticide leaching through macropores is needed.     

Movement of pesticides to surface waters from a heavy clay soil

A field experiment at Cockle Park, Northumberland on a clay loam soil (Dunkeswick series) cropped with winter wheat investigated the effects of drainage and season of application on pesticide movement. Isoproturon, mecoprop, fonofos and trifluralin were applied in two consecutive seasons at normal agricultural rates to three hydrologically isolated plots each of 0.25 ha. Two of the plots were mole-drained and the third was an undrained control. Surfacelayer flow and drainflow from each plot were monitored at 10-min intervals. Samples of flow were analysed for pesticides to evaluate transport of applied chemicals from the site. Despite widely differing properties (K_oc 20–8000 ml g^?1, t_1/2 10–60 days), all four pesticides were found in surface-layer flow and mole drainflow from the site. Maximum concentrations of pesticides in flow ranged from 0.1 to 121 μg litre^?1 (aqueous phase) and < 0.2 to 48 μg litre^?1 (particulate phase). Over two contrasting seasons, total losses of pesticides in flow followed total amounts of flow and were approximately four and five times larger, respectively, in 1990/91 than in 1989/90. The maximum loss occurred from the undrained plot and was 2.8 g isoproturon (0.45% of that applied). Total losses of autumn-applied pesticides from an undrained plot were up to four times greater than losses from a mole-drained plot. Mole drainage decreased movement of pesticides from this slowly permeable soil by reducing the amount of surfacelayer flow. Maximum concentrations of mecoprop and isoproturon in drainflow were 10–20 times larger following spring application than after application in autumn. Bypass flow down soil cracks was an important process by which pesticide was lost from the site, with transport to the drainage system via mole channels (55 cm depth) after less than 0.5 and 6.7 mm net drainage in the two winters.