Pesticide adsorption in the vadose zone: a case study on Eocene and Quaternary materials in Northern France

We present a set of adsorption coefficients measured on various Eocene and Quaternary materials sampled from the vadose zone of a catchment in Northern France for three herbicides, atrazine, isoproturon and metamitron. Some vadose zone materials were found to have higher adsorption coefficients than the topsoil. The adsorption coefficients were strongly dependent on the clay content of the material. From 83% to 97% of the variability in the adsorption coefficients could be explained by a linear relationship to the clay content. Adsorption coefficients normalized for clay content, Kclay, ranged between 1.6 and 17.6 litre kg(-1) for atrazine. Neglecting the adsorption properties of the vadose zone and relying exclusively on Koc values to predict mobility may bias regional or local risk assessment of groundwater contamination by pesticides. More information on the adsorption properties of geological materials should be collected to improve our ability to predict pesticide concentrations in groundwaters.     

Spatial variability in herbicide degradation in the subsurface environment of a groundwater protection zone

The aim of this study was to investigate the spatial variability in degradation and mineralization of atrazine and isoproturon in subsurface samples taken from sandy loam soils overlying gravel terraces which form part of a groundwater protection zone. Percussion drilling was used to obtain samples from 11 boreholes (maximum depth 3 m). Unlabelled atrazine or isoproturon, and ring-14C-labelled atrazine or isoproturon were added to samples, incubated at 25 degrees C for up to 16 weeks, and analyzed for the residual herbicide or [14C]carbon dioxide. All samples showed the potential to degrade these herbicides, although the percentage degradation decreased by a factor of 2-3 from the surface soil to a depth of 3 m. This was associated with a decrease in organic matter content, but there was no change in the potential to mineralize acetate, indicating that specific changes in the catabolic ability of the microbial population occurred with depth. The capacity of samples to mineralize atrazine and isoproturon to carbon dioxide decreased markedly with depth, with no mineralization potential observed at a depth of 80 cm.     

Sorption and desorption of flumioxazin to soil, clay minerals and ion-exchange resin

Flumioxazin adsorption kinetics were described using a Greenville sandy clay loam soil. Adsorption kinetics experiments showed that 72% of total herbicide was absorbed after 1 h of continuous shaking and continued to increase to 78% after 72 h. Flumioxazin adsorption was then tested on seven agriculturally important soils throughout the southern USA. Adsorption isotherms for all soils had K(f) (Freundlich distribution coefficient) values that ranged from 8.8 to 0.4, with many near 1.5. Soil organic matter content was the parameter most highly correlated with flumioxazin adsorption (r(2) = 0.95, P < 0.001). Sorption to clay minerals had K(f) values ranging from 50 for bentonite to 4.7 for kaolinite. However, normalizing K(f) for sorbent surface area revealed that aluminum hydroxide (gibbsite) possessed the greatest flumioxazin sorption per unit area. Sorption to anionic exchange resin (K(f) 676) was greater than cationic exchange resin (K(f) 42). Molecular model calculations were performed to elucidate why sorption was greater to anionic exchangers. These calculations indicated that a region of dense electronegativity exists on the 3-dione moiety of the molecule. This would lead to greater flumioxazin sorption by positively charged surface sites. Desorption isotherms from soil exhibited no effect of hysteresis. Desorption from clay minerals was very rapid and flumioxazin in solution was undetectable after three desorption steps. From these data it was concluded that flumioxazin can become readily available in soil solution with increase in soil water content.     

Degradation of atrazine and isoproturon in the unsaturated zone: a study from Southern England

The potential for degradation of atrazine or isoproturon in the unsaturated zone of two boreholes was studied under laboratory conditions. Intact and uncontaminated samples were obtained from regular depths of 0–16.45 m and 0–9 m using a percussion coring technique. The results showed that the deep unsaturated zone contained micro-organisms capable of degrading atrazine or isoproturon. The rate of degradation was much faster in surface soil than in most unsaturated materials of both boreholes. The amount of atrazine remaining six months after incubation also varied between the two boreholes. A relatively small amount of atrazine was lost from sterilised samples, suggesting a significant role for microbial degradation. The addition of nutrient and energy sources into materials of low degradation capacity did not enhance the degradation of atrazine. Degradation rate was more related to the presence of a competent microbial population rather than to the presence of indigenous organic matter. However, the competent micro-organisms are more likely to be present when the organic matter content is high. The type and activity of these micro-organisms and their physical environment may have considerable influence on atrazine degradation and are likely to be responsible for much of the variation in the rate of degradation observed at different depths. © 1999 Society of Chemical Industry     

Differentiating between physical and chemical constraints on pesticide and water movement into and out of soil aggregates

A laboratory experiment comparing the movement of ³H₂O and [¹⁴C]isoproturon into and release from soil aggregates is described. Small aggregates (2.0–2.4 mm) were prepared from a clay topsoil and maintained at three different initial moisture conditions. A small volume of the radioisotope solution was introduced prior to bathing the aggregates in a 2 mM CaCl₂ solution to represent new rainwater. Whilst the ³H₂O was imbibed by the air-dry aggregates, the pesticide did not follow the water but remained on the surface of the aggregates. This may be related to its sorptive properties and an excess of sorption sites on the sorbent with respect to the sorbate. Increasing the length of exposure of the moist aggregates to [¹⁴C]isoproturon reduced the initial release of the compound into the bathing solution, probably due to diffusion (retarded by sorption) into the aggregates. The diffusion model described by Crank and a non-equilibrium desorption model were used to analyse the ³H₂O and [¹⁴C]isoproturon release curves. This showed that the release of ³H₂O from the dry aggregates was controlled by diffusion. The release of isoproturon was probably controlled by non-equilibrium sorption/desorption from air-dry aggregates and by a combination of non-equilibrium sorption/desorption and diffusion from wet aggregates. © 1999 Society of Chemical Industry     

Degradation of atrazine and isoproturon in surface and sub-surface soil materials undergoing different moisture and aeration conditions

The influence of different moisture and aeration conditions on the degradation of atrazine and isoproturon was investigated in environmental samples aseptically collected from surface and sub-surface zones of agricultural land. The materials were maintained at two moisture contents corresponding to just above field capacity or 90% of field capacity. Another two groups of samples were adjusted with water to above field capacity, and, at zero time, exposed to drying-rewetting cycles. Atrazine was more persistent (t(1/2) = 22-35 days) than isoproturon (t(1/2) = 5-17 days) in samples maintained at constant moisture conditions. The rate of degradation for both herbicides was higher in samples maintained at a moisture content of 90% of field capacity than in samples with higher moisture contents. The reduction in moisture content in samples undergoing desiccation from above field capacity to much lower than field capacity enhanced the degradation of isoproturon (t(1/2) = 9-12 days) but reduced the rate of atrazine degradation (t(1/2) = 23-35 days). This demonstrates the variability between different micro-organisms in their susceptibility to desiccation. Under anaerobic conditions generated in anaerobic jars, atrazine degraded much more rapidly than isoproturon in materials taken from three soil profiles (0-250 cm depth). It is suggested that some specific micro-organisms are able to survive and degrade herbicide under severe conditions of desiccation.     

氯胺嘧草醚在土壤中的吸附行为研究

为评价氯胺嘧草醚的环境安全性,采用批量平衡法测定了氯胺嘧草醚在5种土壤中的吸附-解吸行为,并运用数学模型对其吸附-解吸特性及移动性能进行了分析。结果表明:氯胺嘧草醚在5种土壤中的等温吸附-解吸曲线符合Freundlich模型,吸附常数（Kf值）范围在6.991~18.49之间;不同土壤对其的吸附作用强弱依次为:黑土 > 水稻土 > 褐土 > 潮土 > 红土。氯胺嘧草醚在5种土壤中的有机碳吸附常数（KOC）范围在704.4~1 579之间,推测其在土壤中具有低移动性;薄层层析试验也表明,氯胺嘧草醚在土壤中的移动性较弱。氯胺嘧草醚在5种土壤中的吸附自由能绝对值均小于40 kJ/mol,表明其吸附机理主要是物理吸附。其Kf值与土壤有机质含量、黏粒含量呈正相关,而与土壤pH值呈负相关。解吸试验表明,氯胺醚在其中3种土壤中的解吸过程存在滞后现象。研究表明,在正常使用情况下,氯胺嘧草醚不易对地表水或地下水造成污染风险。     

Desorption of diuron and isoproturon from undispersed clay loam soil

Studies were conducted to investigate the desorption of diuron and isoproturon adsorbed on undispersed clay loam soil, and the influence of residence time in soil on desorption. The soil was treated at 0·6 or 3 mg kg^-1, at 70% moisture content and in the presence of sodium azide to prevent degradation. Measurement of herbicide concentrations in soil solution sampled by means of glass microfibre filters showed that adsorption mainly occurred for one day but long-term sorption proceeded for >two weeks. After a one-day or three-week residence time, soil solution was partly replaced (28%). Measurement of concentrations in solution showed rapid desorption, with equilibria being achieved within 1 h (diuron) or a few hours (isoproturon). After 16 successive desorptions done at 30-min or 12-h intervals, equilibration times tended to be longer. For the short residence time, desorption and long-term sorption could occur simultaneously and equilibration might be faster. Residence time had no significant effect on desorption kinetics nor on the small hysteresis observed for diuron. The aging effect, involving long-term sorption only, decreased the proportion of diuron removed from the soil by successive desorptions but, for isoproturon, desorption frequency and desorption kinetics were more important. © 1997 SCI     

Enhanced soil sorption of methidathion using sewage sludge and surfactants

Batch experiments were carried out to examine the partitioning of an organophosphorus insecticide, methidathion, in non-amended agricultural soil and soil amended with urban sewage sludge and/or different types of surfactant. Kinetic data showed that sewage sludge significantly reduced adsorption rate, whereas amendment of the soil with the cationic surfactant tetradecyltrimethylammonium bromide (TDTMA) at 10 x CMC (critical micellar concentration) increased the adsorption rate by a factor of 10. The adsorption isotherms were evaluated using the Freundlich model. The soil adsorption capacity for methidathion was enhanced by amendment with sewage sludge and even more significantly with TDTMA at 10 x CMC or combined with sewage sludge. TDTMA conferred a high hydrophobic character to the soil, enhancing the adsorption capacity of the rather hydrophobic methidathion. The amendment of soil both with sewage sludge and TDTMA combines the increased hydrophobicity with a higher surfactant retention by organic matter, due to an increase in cation exchange capacity, which promotes even more the adsorption capacity for the insecticide. An anionic surfactant, linear alkylbenzene sulfonate, and the non-ionic Tween 80 only induced a slight modification in the kinetics and adsorption of methidathion.     

Influence of solid/liquid ratio on the experimental frror of sorption coefficients in pesticide/soil systems

The influence of the solid/liquid ratio on the experimental error in the sorption coefficient in pesticide/soil systems was assessed by theoretical analysis. It was assumed that the sorption coefficient is derived from the measured decrease in concentration in the liquid phase of a soil suspension. A first analysis based on systematic errors in the concentration in the liquid phase showed that the relative error in the sorption coefficient is controlled by the product of the solid/liquid ratio and the sorption coefficient (a dimensionless quantity). If this quantity tends to zero, the relative error tends to infinity. A second analysis, based on random errors in the concentration in the liquid phase, gave a similar result. To minimize experimental errors the solid/liquid ratio should be taken as large as possible unless the equilibrium concentration becomes too low to be measured accurately.     

Spatial variability in the degradation rates of isoproturon and chlorotoluron in a clay soil

Thirty separate soil samples were taken from different locations at the Brimstone farm experimental site, Oxfordshire, UK. Incubations of isoproturon under standard conditions (15 °C; ?33 kPa soil water potential) indicated considerable variation in degradation rate in the soil, with the time to 50% loss (DT₅₀) varying from 6 to 30 days. These differences were confirmed in a second comparative experiment in which degradation rates were assessed in 11 samples of the same soil in two separate laboratories using an identical protocol. There was a significant negative linear relationship (r²= 0.746) between the DT₅₀ values and soil pH in this group of soils. In a third experiment, degradation rates of the related compound chlorotoluron were compared with those of isoproturon in 12 separate soil samples, six of which had been stored for several months, and six of which were freshly collected from the field. Degradation of both herbicides occurred more slowly in the stored samples than in the fresh samples but, in all of them, chlorotoluron degraded more slowly than isoproturon, and there was a highly significant linear relationship (r²=0.916) between the respective DT₅₀ values.     

Field experiments for the evaluation of pesticide spray-drift on arable crops

Two distinct approaches were used to characterise spray-drift during the application of atrazine and alachlor to a maize crop. The first consisted in determining the quantities which did not reach their target. A first experiment was carried in 2001 to improve the sampling method. A second experiment in 2002 showed that losses represented 46 and 38% for atrazine and alachlor, respectively. The second approach was to follow the spatiotemporal evolution of the cloud formed during application. The concentrations observed near the application zone during spraying reached 4.5 microg m(-3) for atrazine and 8.5 microg m(-3) for alachlor. With alachlor these concentrations decreased rapidly when increasing distance from the plot or time following treatment, whereas in the case of atrazine they stabilised rapidly (between 0.5 and 0.3 microg m(-3)) both in space and in time. Deposits around the plot were light and slightly higher for alachlor (from 20 to 130 microg m(-2)). Alachlor was more rapidly diluted in space than atrazine, reflecting a differentiated evolution of physical form during the process. Alachlor, being more volatile than atrazine, is quickly transferred to the gaseous phase which was more rapidly dispersed than aerosols.     

Influence of adsorption–desorption phenomena on pesticide run-off from soil using simulated rainfall

The surface run-off of a number of pesticides (diuron, isoproturon, atrazine, alachlor, aclonifen, trifluralin, lindane and simazine), chosen for their range of adsorption behaviours, was studied using simulated rainfall applied to small plots over a short time (one hour). Pesticides were applied together onto bare soil using two different sandy loam soils from Jaillière and Coet Dan sites. The surface run-off samples were collected throughout the running of the event and concentrations of pesticides were measured in both liquid and solid phases. Sorption isotherms for isoproturon and diuron on Jaillière soil as well as eroded particles were measured under equilibrium conditions and compared to their partitioning during surface run-off. At the rainfall intensity used, both soils generated a large load of eroded particles. The average run-off flow rate increased with time for the Jalliére soil, while it remained relatively constant at a higher level for the Coet Dan soil. The concentrations of each pesticide in the run-off samples decreased as the experiments proceeded. The pesticides were classified into two types by their partitioning between the solid and liquid phases. Atrazine, simazine, diuron, isoproturon and alachlor were mainly transported in surface run-off water. By contrast, 90% of trifluralin and aclonifen was adsorbed onto eroded particles. Lindane was intermediate, with a 37% adsorption level. When the contribution of eroded particles was minor, the agrochemical concentrations were inversely proportional to the water flow rate. We have proposed a model that describes the mass of chemicals extracted from soil into surface water during a surface run-off event of a given average duration and flow rate. This model takes into account the dilution of the soil solution and the desorption of chemicals through two parameters called, respectively, the dilution factor and the extraction retardation factor. The desorption kinetic was the limiting step in the surface run-off of weakly sorbed chemicals, such as isoproturon. © 1999 Society of Chemical Industry     

南疆沙漠腹地地温变化特征

利用塔中气象站三年的气象数据,分析了塔中地温的变化特征。结果显示:塔中0～40cm地温年变化规律显著,温度自1月开始迅速上升,在7月达到最高值,达30℃以上,其后又持续下降,冬季最低;80cm以下地温变化平缓,最高、最低温度出现月份逐渐后延,年振幅渐小;在典型晴天、阴天、沙尘天气时,表层地温都是日出前后最低,日出后迅速上升,至午后16时左右达最大值,其后迅速下降,于日落时降至一低值,并在夜间继续缓慢下降;四季0～80cm各层地温夏季﹥秋季﹥春季﹥冬季;天气对地温的影响主要体现在地表温度和浅层地温,至40cm及以下各层几乎无影响,日变化与典型晴天规律相同;阴天和浮尘对地温的影响较小,扬沙和沙尘暴天气对地温影响较大,其影响随深度增加而渐小;各层地温的平均日变化曲线近于正弦曲线,随深度增加地温特征线趋于平缓,极值出现时间逐渐后延。塔中地温的年际、日内变化的逐层性,与沙漠表面风成沙的物理属性有关。     

A method for mapping the distribution of willow at a catchment scale using bi-seasonal SPOT5 imagery

This study showed that seasonal imagery acquired at specific stages of phenology can be used to improve the mapping accuracy of invasive willow at a catchment scale. SPOT5 XI (10 m) satellite imagery was acquired for early autumn and winter to represent the phenological stages of leaf cover and leaf fall respectively. Four classification regimes were evaluated using single‐ and bi‐seasonal composite imagery to determine the most accurate method. Significant spectral noise was found in willow populations, especially in the winter image, due to the effects of undergrowth exposure, shadowing, topography and boundary‐mixed pixels. Two noise reduction techniques were applied to the bi‐seasonal composite image to improve the classification results. The noise‐reduced bi‐seasonal composite image was classified using the spectral angle mapper (SAM) algorithm before importation into a geographical information system. Aerial photography was used to reduce the errors of commission associated with misclassification of pastures. The class accuracy achieved for willow using the method described in this study was 77.5% (Kappa =0.87). The high cost of eradicating willow means that managers must establish priorities for control; this technique can provide a powerful tool for prioritizing control programmes and for monitoring results at a catchment scale.     

Integrated modeling environment for statewide assessment of groundwater vulnerability from pesticide use in agriculture

Atrazine, a herbicide widely used for corn production in the Midwest, has been detected in groundwater of several states, and has been identified as a possible human carcinogen. With the widespread use of pesticides in crop production, and the frequent detection of these chemicals in groundwater, large-scale risk assessments would help water resource managers to identify areas that are more susceptible to contamination and implement practices to ameliorate the problem. This paper presents an integrated, visual and interactive system for predicting potential environmental risks associated with pesticide contamination at spatial scales ranging from fields to landscapes and regions. The interactive system extends the predictive ability of the Pesticide Root Zone Model Release 2.0 (PRZM-2) to a landscape and statewide scale through integration with a geographic information system (GIS), graphical user interface and environmental databases. Predictions of statewide (Iowa) vulnerability of groundwater from atrazine leaching below the unsaturated zone were made to demonstrate the utility of the system, and the results were used in risk assessment. In the example application, atrazine fate and transport were evaluated using long-term climatic data (1980--1989) in combination with several environmental databases (eg STATSGO soils database) and exposure risks were expressed in terms of the probability of the predicted pesticide concentrations exceeding the maximum contaminant level (MCL) for drinking water. The results indicate that the predicted pesticide concentrations were significantly lower than the EPA-established MCL. In addition to providing an interactive environment for landscape-level assessment of potential risks from pesticide leaching, the system significantly reduces the time and resources needed to organize and manipulate data for use with PRZM-2, and provides an analytical framework for evaluating groundwater-leaching impacts of pesticide management practices.     

The pesticide module of the Root Zone Water Quality Model (RZWQM): testing and sensitivity analysis of selected algorithms for pesticide fate and surface runoff

The Root Zone Water Quality Model (RZWQM) is a one-dimensional, numerical model for simulating water movement and chemical transport under a variety of management and weather scenarios at the field scale. The pesticide module of RZWQM includes detailed algorithms that describe the complex interactions between pesticides and the environment. We have simulated a range of situations with RZWQM, including foliar interception and washoff of a multiply applied insecticide (chlorpyrifos) to growing corn, and herbicides (alachlor, atrazine, flumetsulam) with pH-dependent soil sorption, to examine whether the model appears to generate reasonable results. The model was also tested using chlorpyrifos and flumetsulam for the sensitivity of its predictions of chemical fate and water and pesticide runoff to various input parameters. The model appears to generate reasonable representations of the fate and partitioning of surface- and foliar-applied chemicals, and the sorption of weakly acidic or basic pesticides, processes that are becoming increasingly important for describing adequately the environmental behavior of newer pesticides. However, the kinetic sorption algorithms for charged pesticides appear to be faulty. Of the 29 parameters and variables analyzed, chlorpyrifos half-life, the Freundlich adsorption exponent, the fraction of kinetic sorption sites, air temperature, soil bulk density, soil-water content at 33 kPa suction head and rainfall were most sensitive for predictions of chlorpyrifos residues in soil. The latter three inputs and the saturated hydraulic conductivity of the soil and surface crusts were most sensitive for predictions of surface water runoff and water-phase loss of chlorpyrifos. In addition, predictions of flumetsulam (a weak acid) runoff and dynamics in soil were sensitive to the Freundlich equilibrium adsorption constant, soil pH and its dissociation coefficient.     

Microbial aspects of atrazine biodegradation in relation to history of soil treatment

Among 15 soils with different cropping practices, seven which had an history of repeated atrazine applications showed accelerated degradation of this herbicide. By contrast, grassland or agricultural soils with no recorded atrazine application, at least for the last three years, had a low degradation potential. No direct relation was found between the rate of atrazine mineralisation and the size of the microbial biomass. In adapted soils, the amounts of extractable residues were lowered and the very high percentages of radioactivity from [ring-¹⁴C]atrazine recovered as [¹⁴C]carbon dioxide demonstrated that N-dealkylation and deamidation were the only processes for micro-organisms to derive carbon and energy for heterotrophic growth. Kinetics of microbial ¹⁴C accumulation revealed that atrazine ring carbon could be incorporated by direct oxidative condensation with structural components of the bacterial or fungal cell whereas side-chain carbon was preferentially used for biosynthesis of new protoplasmic cell material, as confirmed by the high turnover rate of radiolabelled microbial components. From the determination of the Michaelis–Menten parameters, V_m and K_m in the presence of different selective biocides, it was possible to conclude that fungi were probably less active in atrazine degradation than bacteria and that over years the microbial atrazine-degrading community showed an increased efficiency. © 1999 Society of Chemical Industry