Soil temperature effect in calculating attenuation and retardation factors

The effect of annual variation of daily average soil temperature, at different depths, in calculating pesticides ranking indexes retardation factor and attenuation factor is presented. The retardation factor and attenuation factor are two site-specific pesticide numbers, frequently used as screening indicator indexes for pesticide groundwater contamination potential. Generally, in the calculation of these two factors are not included the soil temperature effect on the parameters involved in its calculation. It is well known that the soil temperature affects the pesticide degradation rate, water-air partition coefficient and water-soil partition coefficient. These three parameters are components of the retardation factor and attenuation factor and contribute to determine the pesticide behavior in the environment. The Arrhenius equation, van't Hoff equation and Clausius-Clapeyron equation are used in this work for estimating the soil temperature effect on the pesticide degradation rate, water-air partition coefficient and soil-water partition coefficient, respectively. These dependence relationships, between results of calculating attenuation and retardation factors and the soil temperature at different depths, can aid to understand the potential pesticide groundwater contamination on different weather conditions. Numerical results will be presented with pesticides atrazine and lindane in a soil profile with 20 degrees C constant temperature, minimum and maximum surface temperatures varying and spreading in the soil profile between -5 and 30 degrees C and between 15 and 45 degrees C.     

Pesticides and groundwater quality protection

A simple approach for ranking the leaching of pesticides from surface soil is presented and tentatively calibrated with field data from an agricultural area. The approach is based on the calculation of a leaching index indicating the proportion of active ingredient, with respect to the quantity applied, leaching from a soil model in a given time interval (one year). In the selected area, 85 wells tapping an unconfined aquifer were sampled for groundwater pesticide residue analysis, in order to explore the index region between leachers and nonleachers.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State-Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, alpha and beta endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino-Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6% leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (alpha-endosulfan), 1.47E-162 (beta-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

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.     

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.     

Degradation and leaching of the herbicides metolachlor and diuron: a case study in an area of Northern Italy

In this work the degradation of the herbicides metolachlor, diuron, monuron and of the metabolites 2-ethyl-6-methylaniline (EMA), and 3,4-dichloroaniline (DCA) was assessed in laboratory experiments on microbiologically active and sterilized soils. Their leaching potentials were calculated, using Gustafson's equation, by determining their mobility (as Koc) and persistence (expressed as DT50). Lysimeter experiments were also conducted to assess the actual leaching of the studied herbicides in a cereal crop tillage area vulnerable to groundwater contamination. The data obtained from the field were compared to the laboratory results. Moreover, some compounds of particular concern were searched for in the groundwater located near the experimental area in order to evaluate actual contamination and to test the reliability of the leaching potential. The GUS index, computed on data from microbiologically active soil, shows monuron as a leacher compound, EMA and DCA as non-leachers, metolachlor and diuron as transient ones. The presence of metolachlor in the groundwater monitored, even at concentrations up to 0.1 mug/l, confirms the possibility that transient compounds can be leached if microbial activity has not completely occurred in active surface soil.     

Influence of input uncertainty on prediction of within-field pesticide leaching risks

Previous research has suggested that pesticide losses at the field scale can be dominated by a small proportion of the field area. The objective of this study was to investigate whether site-specific applications (i.e. avoiding high-risk areas) at the field scale can contribute to a reduction of pesticide leaching despite uncertainty in the underlying model-based leaching risk map. Using a meta-model of the dual-permeability model MACRO, the annual average pesticide leaching concentrations were estimated for 162 sample sites on a 47 ha field. The procedure was repeated for different scenarios describing different patterns of spatial variation of degradation half-lives and the partition coefficient to soil organic carbon. To account for interpolation uncertainty, maps of predicted pesticide leaching risk were produced by the method of sequential Gaussian simulation. The results of the case study show that larger reductions of predicted leaching were achieved by site-specific application than by that of a comparable uniform dose reduction. Hence, site-specific-applications may be a feasible method to reduce pesticide leaching at the field-scale providing that the model approach gives reasonable estimates of the spatial pattern of pesticide leaching.     

Emission, distribution and leaching of methyl isothiocyanate and chloropicrin under different surface containments

The environmental fate of fumigants methyl isothiocyanate (MITC) and chloropicrin (CP) is of great concern for potential air and groundwater contamination while retaining sufficient concentrations for pest control efficacy. The emission, gas phase distribution, leaching, and persistence of MITC and CP were examined in repacked columns filled with sandy soils under three surface conditions: tarp without irrigation, tarp with limited irrigation, and 5-d irrigation without tarp cover. For MITC, cumulative emission constituted 62%, 36%, and 0.3% of the amount applied under tarp without irrigation, tarp with limited irrigation, and 5-d irrigation without tarp surface conditions, respectively. The corresponding cumulative emission losses were 45%, 30%, and 5.4% for CP. During the first 24h after injection, soil air concentrations of the two fumigants were much higher in the 15-25cm depth range than other depths in the soil profile. Small amounts of leaching occurred for both fumigants, indicating potential for groundwater contamination should heavy rain fall or irrigation occurs immediately after soil fumigation. Very small amounts of residual MITC and CP (<2%) were found in the soil 24 days after the experiment. The study clearly showed that atmospheric emission and degradation were the two primary pathways of MITC and CP dissipation during soil fumigation. Emission could be effectively reduced with 5-d irrigation if small leaching is acceptable or be prevented.     

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.     

Leaching of glyphosate and AMPA under two soil management practices in Burgundy vineyards (Vosne-Romanée, 21-France)

Some drinking water reservoirs under the vineyards of Burgundy are contaminated with herbicides. Thus the effectiveness of alternative soil management practices, such as grass cover, for reducing the leaching of glyphosate and its metabolite, AMPA, through soils was studied. The leaching of both molecules was studied in structured soil columns under outdoor conditions for 1 year. The soil was managed under two vineyard soil practices: a chemically treated bare calcosol, and a vegetated calcosol. After 680 mm of rainfall, the vegetated calcosol leachates contained lower amounts of glyphosate and AMPA (0.02% and 0.03%, respectively) than the bare calcosol leachates (0.06% and 0.15%, respectively). No glyphosate and only low amounts of AMPA (<0.01%) were extracted from the soil. Glyphosate, and to a greater extent, AMPA, leach through the soils; thus, both molecules may be potential contaminants of groundwater. However, the alternative soil management practice of grass cover could reduce groundwater contamination by the pesticide.     

A screening method for preliminary assessment of risk to groundwater from land-applied chemicals

A simple mathematical model for initial screening is presented that can aid in evaluating the relative risk to groundwater from applying nonpolar synthetic organic chemicals to soil. The basic premise is that the magnitude of the quotient of the chemical concentration of the water entering the aquifer and the maximum allowable concentration (as established by EPA or Health Departments) represents the health risk of a chemical. The chemical concentration of the soil water is estimated based on conservative, simplifying assumptions and requires only readily available data such as: basic soil properties (organic matter and saturated hydraulic conductivity), organic chemical properties (octanol-water partition coefficient and degradation rate) and environmental factors (recharge rate and depth to groundwater).The methodology was applied to assess the relative risk of organic chemicals in municipal sewage sludge and pesticides applied to agricultural land. The results are realistic.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

Leaching and half-life of the herbicide tebuthiuron on a recharge area of Guarany aquifer in sugarcane fields in Brazil

This study was undertaken to evaluate the degradation and mobility of the herbicide tebuthiuron (N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N'-dimethylurea) in soil under field conditions, and its potential for leaching and groundwater contamination. A watershed, Espraiado, located over a recharge area in Brazil, was chosen for soil and water studies. At Espraiado, water samples were collected from seven wells at intervals of three months from March 2004 to June 2006 and analyzed for tebuthiuron. Other samples were taken from city wells located outside of the recharge area. To assess the potential movement to the aquifer, tebuthiuron was also applied to trial plots at the recommended label rate of 1.0 kg/ha a.i. in May of 2004, with and without sugarcane coverage, on sandy soil. Soil samples were collected during the years of 2004 and 2005, at depths intervals of 20 cm from soil surface down to 120 cm and analyzed for tebuthiuron at zero, 3, 30, 60, 90, 120, 150, 180, 240, and 300 days after application. There was no clear effect of sugarcane coverage on the tebuthiuron degradation in soils, but it moved faster into the soil where there was no cover. After 180 days there were no measurable residues in the soil, and tebuthiuron was not found below 40 cm depth in any time. Tebuthiuron had a half-life of 20 days under those conditions. No tebuthiuron residue was found in ground water samples at any sampling time.     

Leaching and half-life of the herbicide tebuthiuron on a recharge area of Guarany aquifer in sugarcane fields in Brazil

This study was undertaken to evaluate the degradation and mobility of the herbicide tebuthiuron (N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N′-dimethylurea) in soil under field conditions, and its potential for leaching and groundwater contamination. A watershed, Espraiado, located over a recharge area in Brazil, was chosen for soil and water studies. At Espraiado, water samples were collected from seven wells at intervals of three months from March 2004 to June 2006 and analyzed for tebuthiuron. Other samples were taken from city wells located outside of the recharge area. To assess the potential movement to the aquifer, tebuthiuron was also applied to trial plots at the recommended label rate of 1.0 kg/ha a.i. in May of 2004, with and without sugarcane coverage, on sandy soil. Soil samples were collected during the years of 2004 and 2005, at depths intervals of 20 cm from soil surface down to 120 cm and analyzed for tebuthiuron at zero, 3, 30, 60, 90, 120, 150, 180, 240, and 300 days after application. There was no clear effect of sugarcane coverage on the tebuthiuron degradation in soils, but it moved faster into the soil where there was no cover. After 180 days there were no measurable residues in the soil, and tebuthiuron was not found below 40 cm depth in any time. Tebuthiuron had a half-life of 20 days under those conditions. No tebuthiuron residue was found in ground water samples at any sampling time.     

Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brévilles, France

The objective of this study was to identify the main controls on atrazine leaching through luvisols and calcisols overlying fissured limestone using the dual-permeability model MACRO. The model parameterisation was based on a combination of direct measurements (e.g. hydraulic properties, adsorption and degradation), literature data and calibration against bromide leaching experiments in field plots. A Monte Carlo sensitivity analysis was carried out for a typical application pattern, considering two different depths of unsaturated limestone (15 and 30 m). MACRO calibrations to the field experiments demonstrated the occurrence of strong macropore flow in the luvisol, while transport in the calcisol could be described by the advection-dispersion equation. MACRO simulations of tritium and atrazine leaching qualitatively matched tritium concentration profiles measured in the limestone and atrazine concentrations measured in piezometers and in aquifer discharge via a spring. The sensitivity analysis suggested that the thickness of the limestone, as well as the transport properties and processes occurring in the unsaturated rock (e.g. matrix vs. fissure flow) will have little significant long-term effect on atrazine leaching, mainly because degradation is very slow in the limestone. No mineralization of atrazine was detected in one-year incubations and a mean half-life of 10 years was assumed in the simulations. Instead, processes occurring in the soil exerted the main control on predicted atrazine leaching, especially variations in the degradation rate and the strength of sorption and macropore flow. However, fissure flow in unsaturated rock is expected to exert a much more significant control on groundwater contamination for compounds that degrade more readily in the deep vadose zone.     

Model approach for estimating potato pesticide bioconcentration factor

We presented a model that estimates the bioconcentration factor (BCF) of pesticides in potatoes supposing that the pesticide in the soil solution is absorbed by the potato by passive diffusion, following Fick's second law. The pesticides in the model are nonionic organic substances, traditionally used in potato crops that degrade in the soil according to a first-order kinetic equation. This presents an expression that relates BCF with the pesticide elimination rate by the potato, with the pesticide accumulation rate within the potato, with the rate of growth of the potato and with the pesticide degradation rate in the soil. BCF was estimated supposing steady state equilibrium of the quotient between the pesticide concentration in the potato and the pesticide concentration in the soil solution. It is suggested that a negative correlation exists between the pesticide BCF and the soil sorption partition coefficient. The model was built based on the work of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108], in which an expression to calculate the diffusivity of persistent organic substances in potatoes is presented. The model consists in adding to the expression of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108] the hypothesis that the pesticide degrades in the soil. The value of BCF suggests which pesticides should be monitored in potatoes.