The mobility of thiobencarb and fipronil in two flooded rice-growing soils

The mobility of the rice pesticides thiobencarb (S-[(4-chlorophenyl) methyl] diethylcarbamothioate) and fipronil ([5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]pyrazole) were investigated in the glasshouse under flooded conditions using two Australian rice-growing soils. When using leakage rates of 10 mm day(-1), less than 20% of applied thiobencarb and fipronil remained in the water column after 10 days due to rapid transfer to the soil phase. Up to 70% and 65% of the applied thiobencarb and fipronil, respectively, were recovered from the 0-1 cm layer of soils. Only 5-7% of each pesticide was recovered from the 1-2 cm layer, and less than 2% was recovered from each 1 cm layer in the 2-10 cm region of the soils. Analysis of the water leaking from the base of the soil cores showed between 5-10% of the applied thiobencarb and between 10-20% of the applied fipronil leaching from the soil cores. The high levels of pesticide in the effluent was attributed to preferential flow of pesticide-laden water via soil macropores resulting from the wetting and drying process, worm holes and root channels.     

The mobility of thiobencarb and fipronil in two flooded rice-growing soils

The mobility of the rice pesticides thiobencarb (S-[(4-chlorophenyl) methyl] diethylcarbamothioate) and fipronil ([5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]pyrazole) were investigated in the glasshouse under flooded conditions using two Australian rice-growing soils. When using leakage rates of 10 mm day^?1, less than 20% of applied thiobencarb and fipronil remained in the water column after 10 days due to rapid transfer to the soil phase. Up to 70% and 65% of the applied thiobencarb and fipronil, respectively, were recovered from the 0–1 cm layer of soils. Only 5–7% of each pesticide was recovered from the 1–2 cm layer, and less than 2% was recovered from each 1 cm layer in the 2–10 cm region of the soils. Analysis of the water leaking from the base of the soil cores showed between 5–10% of the applied thiobencarb and between 10–20% of the applied fipronil leaching from the soil cores. The high levels of pesticide in the effluent was attributed to preferential flow of pesticide-laden water via soil macropores resulting from the wetting and drying process, worm holes and root channels.     

Increasing the efficiency of solute leaching: impacts of flow interruption with drainage of the “preferential flow paths”

Most soils contain preferential flow paths that can impact on solute mobility. Solutes can move rapidly down the preferential flow paths with high pore-water velocities, but can be held in the less permeable region of the soil matrix with low pore-water velocities, thereby reducing the efficiency of leaching. In this study, we conducted leaching experiments with interruption of the flow and drainage of the main flow paths to assess the efficiency of this type of leaching. We compared our experimental results to a simple analytical model, which predicts the influence of the variations in concentration gradients within a single spherical aggregate (SSA) surrounded by preferential flow paths on leaching. We used large (length: 300 mm, diameter: 216 mm) undisturbed field soil cores from two contrasting soil types. To carry out intermittent leaching experiments, the field soil cores were first saturated with tracer solution (CaBr₂), and background solution (CaCl₂) was applied to mimic a leaching event. The cores were then drained at 25- to 30-cm suction to empty the main flow paths to mimic a dry period during which solutes could redistribute within the undrained region. We also conducted continuous leaching experiments to assess the impact of the dry periods on the efficiency of leaching. The flow interruptions with drainage enhanced leaching by 10–20% for our soils, which was consistent with the model's prediction, given an optimised “equivalent aggregate radius” for each soil. This parameter quantifies the time scales that characterise diffusion within the undrained region of the soil, and allows us to calculate the duration of the leaching events and interruption periods that would lead to more efficient leaching. Application of these methodologies will aid development of strategies for improving management of chemicals in soils, needed in managing salts in soils, in improving fertiliser efficiency, and in reclaiming contaminated soils.     

Interactions of tillage and rainfall on atrazine leaching under field and laboratory conditions

Laboratory studies were conducted to evaluate effects of tillage reversal and rainfall on ¹⁴C-atrazine (2-chloro4-ethylamino-6-isopropylamino- -triazine) leaching patterns. Twelve intact soil cores (16 cm dia x 20 cm deep) were collected from 8-yr no-till (NT) fields. Half the cores were tilled (5 cm deep) prior to ¹⁴C-atrazine treatment (2.7 mg core⁻¹) to all cores. All cores received two rains (27 mm rain in 1.5 h, one day after application followed, two days later, by a 17 mm rain in 2.5 h) and leachate was collected and analyzed for atrazine. These rains simulated the timing, amount and duration of natural rainfall events from a tillage reversal field study. During the first high inte ity rainfall event, a pulse (2.1 μg L-1) of atrazine leached through tilled cores while leaching rate was linear and decreased (1.25 to 0.9 μg L-1) through un-tilled cores. Leaching rate was linear for both the tilled and un-tilled cores during the second rain. Less atrazine was left in the surface 5 cm of tilled soil than un-tilled after the two rains. Results confirmed field observations and suggested that when tillage is reversed on well structured soils, pesticide leaching may increase relative to un-tilled soil but these effects are probably confined to the first rain events after application only.     

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.     

Aldicarb and carbofuran transport in a Hapludalf influenced by differential antecedent soil water content and irrigation delay

Pesticide use in agroecosystems can adversely impact groundwater quality via chemical leaching through soils. Few studies have investigated the effects of antecedent soil water content (SWC) and timing of initial irrigation (TII) after chemical application on pesticide transport and degradation. The objectives of this study were to investigate the effects of antecedent soil water content (wet vs dry) and timing of initial irrigation (0h Delay vs 24h Delay) on aldicarb [(EZ)-2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime] and carbofuran [2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate] transport and degradation parameters at a field site with Menfro silt loam (fine-silty, mixed, superactive, mesic Typic Hapludalf) soils. Aldicarb and carbofuran were applied to plots near field capacity (wet) or near permanent wilting point (dry). Half of the dry and wet plots received irrigation water immediately after chemical application and the remaining plots were irrigated after a 24h Delay. The transport and degradation parameters were estimated using the method of moments. Statistical significance determined for SWC included averages across TII levels, and significance determined for TII included averages across SWC levels. For the dry treatment, aldicarb was detected 0.10 m deeper (P<0.01) on two of the four sampling dates and carbofuran was detected at least 0.10 m deeper (P<0.05) on all of the sampling dates compared to the wet treatment. Pore water velocity was found to be higher (P<0.10) in the dry vs wet treatments on three of four dates for aldicarb and two of four dates for carbofuran. Retardation coefficients for both pesticides showed similar evidence of reduced values for the dry vs wet treatments. These results indicate deeper pesticide movement in the initially dry treatment. For aldicarb and carbofuran, estimated values of the degradation rate were approximately 40-49% lower in the initially dry plots compared to the initially wet plots, respectively. When the initial irrigation was delayed for 24h, irrespective of antecedent moisture conditions, a 30% reduction in aldicarb degradation occurred. This study illustrates the deeper transport of pesticides and their increased persistence when applied to initially dry soils.     

Degradation of fenamiphos in soils collected from different geographical regions: the influence of soil properties and climatic conditions

The persistence of fenamiphos (nematicide) in five soils collected from different geographical regions such as Australia, Ecuador and India under three temperature regimes (18, 25 and 37 degrees C) simulating typical environmental conditions was studied. The effect of soil properties (soil pH, temperature and microbial biomass) on the degradation of fenamiphos was determined. The rate of degradation increased with increase in temperature. Fenamiphos degradation was higher at 37 degrees C than at 25 and 18 degrees C (except under alkaline pH). The degradation pathway differed in different soils. Fenamiphos sulfoxide (FSO) was identified as the major degradation product in all the soils. Fenamiphos sulfone (FSO2), and the corresponding phenols: fenamiphos phenol (FP), fenamiphos sulfoxide phenol (FSOP) and fenamiphos sulfone phenol (FSO2P) were also detected. The degradation of fenamiphos was faster in the alkaline soils, followed by neutral and acidic soils. Under sterile conditions, the dissipation of the pesticide was slower than in the non-sterile soils suggesting microbial role in the pesticide degradation. The generation of new knowledge on fenamiphos degradation patterns under different environmental conditions is important to achieve better pesticide risk management.     

Degradation of fenamiphos in soils collected from different geographical regions: The influence of soil properties and climatic conditions

The persistence of fenamiphos (nematicide) in five soils collected from different geographical regions such as Australia, Ecuador and India under three temperature regimes (18, 25 and 37°C) simulating typical environmental conditions was studied. The effect of soil properties (soil pH, temperature and microbial biomass) on the degradation of fenamiphos was determined. The rate of degradation increased with increase in temperature. Fenamiphos degradation was higher at 37°C than at 25 and 18°C (except under alkaline pH). The degradation pathway differed in different soils. Fenamiphos sulfoxide (FSO) was identified as the major degradation product in all the soils. Fenamiphos sulfone (FSO₂), and the corresponding phenols: fenamiphos phenol (FP), fenamiphos sulfoxide phenol (FSOP) and fenamiphos sulfone phenol (FSO₂P) were also detected. The degradation of fenamiphos was faster in the alkaline soils, followed by neutral and acidic soils. Under sterile conditions, the dissipation of the pesticide was slower than in the non-sterile soils suggesting microbial role in the pesticide degradation. The generation of new knowledge on fenamiphos degradation patterns under different environmental conditions is important to achieve better pesticide risk management.     

Sorption and leaching potential of acidic herbicides in Brazilian soils

Leaching of acidic herbicides (2,4-D, flumetsulam, and sulfentrazone) in soils was estimated by comparing the original and modified AF (Attenuation Factor) models for multi-layered soils (AFi). The original AFi model was modified to include the concept of pH-dependence for Kd (sorption coefficient) based on pesticide dissociation and changes in the accessibility of soil organic functional groups able to interact with the pesticide. The original and modified models, considering soil and herbicide properties, were applied to assess the leaching potential of selected herbicides in three Brazilian soils. The pH-dependent Kd values estimated for all three herbicides were observed to be always higher than pH-independent Kd values calculated using average Koc data, and therefore the original AFi model overestimated the overall leaching potential for the soils studied.     

Evaluation of soil temperature effect on herbicide leaching potential into groundwater in the Brazilian Cerrado

The effect of annual variations in the daily average soil temperatures, at different depths, on the calculation of pesticide leaching potential indices is presented. This index can be applied to assess the risk of groundwater contamination by a pesticide. It considers the effects of water table depth, daily recharge net rate, pesticide sorption coefficient, and degradation rate of the pesticide in the soil. The leaching potential index is frequently used as a screening indicator in pesticide groundwater contamination studies, and the temperature effect involved in its calculation is usually not considered. It is well known that soil temperature affects pesticide degradation rates, air-water partition coefficient, and water-soil partition coefficient. These three parameters are components of the attenuation and retardation factors, as well as the leaching potential index, and contribute to determine pesticide behavior in the environment. The Arrhenius, van't Hoff, and Clausius-Clapeyron equations were used in this work to estimate the soil temperature effect on pesticide degradation rate, air-water partition coefficient, and water-soil partition coefficient, respectively. The relationship between leaching potential index and soil temperature at different depths is presented and aids in the understanding of how potential pesticide groundwater contamination varies on different climatic conditions. Numerical results will be presented for 31 herbicides known to be used in corn and soybean crops grown on the municipality of S?o Gabriel do Oeste, Mato Grosso do Sul State, Brazil.     

Characterization of non-extractable residues of the fungicide dithianon in soil using 13C/14C-labelling techniques

The fate of the (14)C-labelled fungicide dithianon in soil is characterized by the formation of non-extractable, "bound" residues of approximately 63% of applied amount in 64 d. Humic acids containing these "bound" residues were isolated after conducting degradation studies of the active ingredient in an orthic luvisol under standardized conditions. In the same way, (13)C-labelled dithianon was incubated in an artificial soil which was produced by humification of (13)C-depleted straw in an incinerated soil. The "bound" residues of the (13)C-labelled dithianon in the humic acid fraction of the artificial soil were analyzed using (13)C-NMR techniques. There was no evidence of a covalent bonding of the residues to the humic substances. Results of polarity gradient high performance thin layer chromatography (AMD-HPTLC) of "bound" residues of the (14)C-labelled dithianon in the humic acid fraction indicate a sequestration process of metabolites into the humic substance as a possible binding mechanism.     

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.     

Spatial and temporal distribution of the leaching of surface applied tracers from an irrigated monolith of a loamy vineyard soil

Fresh water scarcity is an increasing problem worldwide. Strategies to alleviate water scarcity include the use of low-quality water for irrigation. The risk of groundwater contamination by pollutants in this water is affected by soil heterogeneity and preferential flow. These risk factors can be assessed by measuring the spatio-temporal redistribution of uniformly applied water and solutes. We placed a soil monolith (height 29 cm) from an Australian vineyard on a 100-cell multi-compartment sampler (MCS). At this vineyard, treated wastewater is used in response to the severe shortage of water in the summer. We studied the leaching risk associated with heterogeneous or preferential flow by irrigating the soil column with 24 applications to simulate one year. We applied simulated rainfall as well as wastewater (which contained chloride) during summer while relying on rainfall only in winter. We compared the chloride leaching with the leaching of bromide, which was applied during one of the applications as a pulse. During the entire simulated year, leaching of solutes from the monolith was measured. The results indicate that the assumption of uniform flow would underestimate the risk for the fresh groundwater reserves: 25 % of the solutes are transported though 6 % of the soil’s cross-section. The spatial distribution of drainage and solute leaching varied little during the experiment. Consequently, the mass flux density pattern of the bromide pulse was comparable to that of the repeatedly applied chloride. However, the MCS data suggested lateral ‘escape’ from chloride to non-mobile areas, which means in the long run, considerable quantities of these solutes can build up in areas that do not receive irrigation water.     

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.     

Leaching of the organophosphorus nematicide fosthiazate

Fosthiazate is an organophosphorus nematicide which was recently included in Annex I of the Directive 91/414/EEC under the clause that it should be used with special care in soils vulnerable to leaching. Thus, the leaching of fosthiazate was investigated in columns packed with three different soils which represented situations of high (site 2), intermediate (site 1) and low (site 3) leaching potential. The recommended dose of fosthiazate was applied at the surface of the soil columns and fosthiazate fate and transport was investigated for the next two months. Fosthiazate concentrations in the leachate collected from the bottom of the columns packed with soil from site 2 exceeded 0.1 microgl(-1) in most cases. This soil was characterized as acidic, indicating longer fosthiazate persistence, with low organic matter content, indicating weak adsorption, thus representing a situation vulnerable to leaching. In contrast, the lowest concentrations of fosthiazate in the leachate were evident in the columns packed with soil from site 3. This soil was characterized as alkaline, indicating faster degradation, with higher organic matter content, indicating stronger adsorption, thus representing a situation not favoring leaching of fosthiazate. The highest concentration of fosthiazate in the leachate from the columns packed with soil from site 2 was 3.44 microgl(-1) compared to 1.17 and 0.16 microgl(-1), which were the corresponding maximum values measured in columns packed with soil from sites 1 and 3, respectively. The results of the current study further suggest that fosthiazate is mobile in soil and can leach under conducive soil conditions like acidic soils with low organic matter content.     

Monod kinetics rather than a first-order degradation model explains atrazine fate in soil mini-columns: Implications for pesticide fate modelling

Pesticide transport models commonly assume first-order pesticide degradation kinetics for describing reactive transport in soil. This assumption was assessed in mini-column studies with associated batch degradation tests. Soil mini-columns were irrigated with atrazine in two intermittent steps of about 30 days separated by 161 days application of artificial rain water. Atrazine concentration in the effluent peaked to that of the influent concentration after initial break-through but sharply decreased while influx was sustained, suggesting a degradation lag phase. The same pattern was displayed in the second step but peak height and percentage of atrazine recovered in the effluent were lower. A Monod model with biomass decay was successfully calibrated to this data. The model was successfully evaluated against batch degradation data and mini-column experiments at lower flow rate. The study suggested that first-order degradation models may underestimate risk of pesticide leaching if the pesticide degradation potential needs amplification during degradation.     

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

The impact of rice plant roots on the reducing conditions in flooded rice soils

The impact of oxygen diffusion from plant roots on the soil redox in the root zone in flooded rice bays was investigated using two Australian rice growing soils. The rates of production of Fe(II) and Mn(II) in pore water resulting from the reduction of soil minerals was used to gauge the extent of development of anaerobic conditions and the time taken for equilibrium to establish. Soil concentrations of readily reducible Fe were 13–28 times greater than Mn, making Fe a more reliable indicator of redox conditions than Mn. In addition, Mn(II) concentrations reached equilibrium far more rapidly than Fe, which made the identification of any contribution to soil redox by oxygen diffusing from rice plant roots difficult to observe. Dissection of soil cores showed that more than 80% of the rice root mass occurred in the top 4 cm of soil, suggesting that any contribution roots may make to the redox potential of the flooded soils would occur in this region. However, studies conducted indicated that the diffusion of oxygen from the surface floodwater into soil pore water in the 2.5 cm layer of soil was so substantial that it would mask any contribution made by rice plant roots to the overall soil redox in this root zone.     

Effect of industrial waste products on phosphorus mobilisation and biomass production in abattoir wastewater irrigated soil

This study evaluated the effect of alkaline industrial by-products such as flyash (FA) and redmud (RM) on phosphorus (P) mobilisation in abattoir wastewater irrigated soils, using incubation, leaching and plant growth (Napier grass [Pennisetum purpureum]) experiments. The soil outside the wastewater irrigated area was also collected and treated with inorganic (KH₂PO₄ [PP]) and organic (poultry manure [PM]) P treatments, to study the effect of FA and RM on P mobilisation using plant growth experiment. Among the amendments, FA showed the highest increase in Olsen P, oxalic acid content and phosphatase activity. The highest increase in Olsen P for PM treated non-irrigated soils showed the ability of FA and RM in mobilising organic P better than inorganic P (PP). There was over 85 % increase in oxalic acid content in the plant growth soils compared to the incubated soil, showing the effect of Napier grass in the exudation of oxalic acid. Both amendments (FA and RM) showed an increase in phosphatase activity at over 90 % at the end of the 5-week incubation period. The leaching experiment indicated a decrease in water soluble P thereby ensuring the role of FA and RM in minimising P loss to water bodies. FA and RM showed an increase in plant biomass for all treatments, where FA amended soil showed the highest increase as evident from FA’s effect on Olsen P. Therefore, the use of FA and RM mobilised P in abattoir wastewater irrigated soils and increased biomass production of Napier grass plants through root exudation of oxalic acid.