Behavior of bensulfuron-methyl in an agricultural alkaline soil

A field experiment to determine the available bensulfuron-methyl (BSM) in the upper soil layer was conducted in an agricultural area in the South of Spain. To facilitate herbicide analysis, two application rates were employed, 200 g ha^?1 and 5 kg ha^?1. Samples of upper soil and soil solution were collected. Soil solution was sampled by means of metallic samplers, placed at a depth of 35 cm. In the plots receiving the lower dose ceramic suction, porous cups were also installed. Results from soil solution samples showed that the maximum BSM concentration was found after 8-10 days for the high irrigation supply (945 mm) and after 18-25 days for the lower irrigation regime (405 mm). The mathematical model FOCUSPELMO 1.1.1 was applied to interpret the data obtained in the field experiments. In general, there was a reasonable agreement between experimental and simulated data for soil samples, although the model did not acceptably predict herbicide concentrations in water soil samples. Ceramic cups sampled a higher soil water volume and more frequently than did the metallic samplers. However some variable results were attributed to preferential flow.     

Microbiological characterization of the biological treatment of aircraft paint stripping wastewater

Leaching rates of the herbicide dichlorprop [(+/--2-(2,4-dichlorophenoxy)propanoic acid] and nitrate were measured together in field lysimeters containing undisturbed clay and peat soils. The purpose of the study was to investigate the leaching pattern of the two solutes in structured soils under different precipitation regimes. Spring barley (Hordeum distichum L.) was sown on each monolith and fertilized with 100 kg N ha(-1). Dichlorprop was applied at a rate of 1.6 kg active ingredient (a.i.) ha(-1). Each soil type received supplemental irrigation at two levels ('average' and 'worst-case'), giving total water inputs (irrigation and precipitation) of 664 and 749 mm year(-1), respectively. The larger water input approximately doubled the nitrate loads, from, on average, 11.6 to 21.8 kg N ha(-1) year(-1) in the clay soil and from 37.6 to 65.4 kg N ha(-1) year(-1) in the peat soil. In contrast, dichlorprop leaching was reduced by more than one order of magnitude when the water input was increased, from average amounts of 3.22 to 0.26 g a.i. ha(-1) during an S-month period in the clay and from 28.9 to 2.67 g a.i. ha(-1) in the peat. This leaching pattern of dichlorprop was explained in terms of preferential flow. The dried-out topsoil of 'average' watered monoliths may have allowed water flow in cracks, thus moving some of the herbicide rapidly through the topsoil to the subsoil. Once the compound reached the subsoil, degradation rates would be reduced and the herbicide residues would be stored for later leaching. Nitrate was presumably more evenly distributed in the soil matrix; therefore, water rapidly moving through macropores would not carry significant amounts of nitrate. In contrast, leaching would occur more evenly through the soil matrix, causing larger nitrate loads in the 'worst-case' watered monoliths. These results show that wet years may constitute a worst case scenario in terms of nitrate leaching, but not pesticide leaching, if macropore flow exerts a significant influence on leaching.     

Dissipation of alachlor in cotton plant, soil and water and its bioaccumulation in fish

Dissipation of alachlor in soil and plant in field condition (cotton cropping system), and in soil, water and fish in simulated model ecosystem was investigated. The acetanilide herbicide, alachlor (50% w/w EC) was applied as pre-emergence at 2.5 and 5.0 kg a.i.ha(-1) three days after sowing the cotton seeds in the field. Soil and plant samples were collected at intervals and analyzed for alachlor residues. To study the fate of alachlor in water and fish, a simulated model ecosystem was constructed and fish was introduced one day after herbicide application. The dissipation of alachlor in water and soil and bioaccumulation in fish was observed in model ecosystem. At harvest, cotton lint and seed samples were found to contain alachlor well below the detectable level. However, trace amounts of residues were found in cotton oil. After harvest of cotton, coriander (Coriandrum sativum) and edible amaranth (Amaranthus mangostanus L.) were raised for herbicide bioassay. The green leafy vegetable samples did not show any toxic symptoms of alachlor residues.     

Effects of glyphosate and foliar amendments on activity of microorganisms in the soybean rhizosphere

A field study was conducted to determine the effects of glyphosate on microbial activity in the rhizosphere of glyphosate-resistant (GR) soybean and to evaluate interactions with foliar amendments. Glyphosate at 0.84 kg ae ha(-1) was applied GR soybean at the V4-V5 development stages. Check treatments included a conventional herbicide tank mix (2003 study only) and no herbicides (hand-weeded). Ten days after herbicide application, a commercially available biostimulant and a urea solution (21.0% N) were applied to soybean foliage at 33.5 mL ha(-1) and 9.2 kg ha(-1), respectively. Soil and plant samples were taken 0, 5, 10, 15, 20 and 25 days after herbicide application then assayed for enzyme and respiration activities. Soil respiration and enzyme activity increased with glyphosate and foliar amendment applications during the 2002 growing season; however, similar increases were not observed in 2003. Contrasting cumulative rainfall between 2002 and 2003 likely accounted for differences in soil microbial activities. Increases in soil microbial activity in 2002 suggest that adequate soil water and glyphosate application acted together to increase microbial activity. Our study suggests that general soil microbial properties including those involving C and N transformations are not sensitive enough to detect effects of glyphosate on rhizosphere microbial activity. Measurements of soil-plant-microbe relationships including specific microbial groups (i.e., root-associated Fusarium spp.) are likely better indicators of impacts of glyphosate on soil microbial ecology.     

Runoff and leaching of atrazine and alachlor on a sandy soil as affected by application in sprinkler irrigation

Rainfall simulation was used with small packed boxes of soil to compare runoff of herbicides applied by conventional spray and injection into sprinkler-irrigation (chemigation), under severe rainfall conditions. It was hypothesized that the larger water volumes used in chemigation would leach some of the chemicals out of the soil surface rainfall interaction zone, and thus reduce the amounts of herbicides available for runoff. A 47-mm rain falling in a 2-hour event 24 hours after application of alachlor (2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)-acetamide) and atrazine (6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2, 4-diamine) was simulated. The design of the boxes allowed a measurement of pesticide concentrations in splash water throughout the rainfall event. Initial atrazine concentrations exceeding its' solubility were observed. When the herbicides were applied in 64,000 L/ha of water (simulating chemigation in 6.4 mm irrigation water) to the surface of a Tifton loamy sand, subsequent herbicide losses in runoff water were decreased by 90% for atrazine and 91% for alachlor, as compared to losses from applications in typical carrier water volumes of 187 L/ha. However, this difference was not due to an herbicide leaching effect but to a 96% decrease in the amount of runoff from the chemigated plots. Only 0.3 mm of runoff occurred from the chemigated boxes while 7.4 mm runoff occurred from the conventionally-treated boxes, even though antecedent moisture was higher in the former. Two possible explanations for this unexpected result are (a) increased aggregate stability in the more moist condition, leading to less surface sealing during subsequent rainfall, or (b) a hydrophobic effect in the drier boxes. In the majority of these pans herbicide loss was much less in runoff than in leachate water. Thus, in this soil, application of these herbicides by chemigation would decrease their potential for pollution only in situations where runoff is a greater potential threat than leaching.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT(50) values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, (14)C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 +/- 0.002% and 0.005 +/- 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

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.     

Porous cups for pesticides monitoring in soil solution — Laboratory tests

In this study, preliminary tests were conducted aiming to validate the use of ceramic porous cup for collecting soil water samples and monitoring pesticides contents, as usually made for nitrates. Interactions between porous cup and pesticides were examined under different experimental conditions for three herbicides (atrazine, isoproturon, 2,4-D) and one insecticide (carbofuran).

The results showed that ceramic was not inert for pesticides : as much as 80% of the applied pesticide could be retained during the flowing of the first tenth milliliters of solution. Interactions were attributed to sorption and “screening” of molecules by the porous walls and were related to the ionic character of pesticides. However, retention was not irreversible, since pesticides were quickly released by rinsing with distilled water.

After these tests, porous ceramic cups could be considered as suitable samplers for pesticide determinations in soil solution, contingent on gaining further informations about soil - porous cup - pesticide interactions.     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 micro g g(-1). The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4-6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

Pesticide storage and release in unsaturated soil in Illinois, USA.

The chemical fate and movement of pesticides may be subject to transient storage in unsaturated soils during periods of light rainfall, and subsequent release into shallow groundwater by increased rainfall. The objective of this study was to conduct field-scale experiments to determine the relative importance of transient storage and subsequent release of agrichemicals from the vadose zone into potential aquifers. Two field-scale experiments were conducted under a rain exclusion shelter. In the 1x experiment, atrazine and chlorpyrifos were applied at application-rate equivalents (1.6 kg ha(-1) and 1.3 kg ha(-1), respectively). In the 4x experiment, atrazine was applied in an amount that was four times greater than that usually applied to fields (6.7 kg ha(-1)). Water was either applied to simulate rain or withheld to simulate dry periods. In the 1x experiment, atrazine was detected in the water samples whereas chlorpyrifos was not detected in the majority of the samples. The dry period imposed on the treatment plot did not appear to result in storage of the chemicals, whereas the wet period resulted in greater leaching of atrazine, although the concentrations remained less than the Maximum Contaminant Level of 3 microg L(-1). Both chemicals were detected in soil samples collected from a 20- to 30-cm depth, but it appeared that both chemicals dissipated before the field experiment was concluded. It appeared that the one-time application of atrazine and chlorpyrifos at the label rates did not result in a sufficient mass to be stored and flushed in significant concentrations to the saturated zone. When atrazine was applied at 4x and a longer drought period was imposed on the treatment plot, the resulting concentrations of dissolved atrazine were still less than 3 microg L(-1) . Atrazine was detected in only the near-surface (0 to 15 cm) soil samples and the herbicide dissipated before the onset of the dry period in the treatment plot. The results of this field study demonstrated that atrazine and chlorpyrifos were not sufficiently persistent to be stored and then released in significantly large concentrations to the saturated zone. The dissipation half-life of atrazine in the 4x application was about 44 days. This study, in addition to others, suggested that atrazine may be less persistent in surface soil than has been generally reported.     

Atrazine sorption and fate in a Ultisol from humid tropical Brazil

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.     

The input-output balance of cadmium in a paddy field of Tokyo

Field monitoring was practiced from 2001 to 2003 to evaluate the input (irrigation, atmospheric deposition, and fertilizer application) and the output (uptake and accumulation into the above-ground biomass of rice plants and leaching) of cadmium (Cd) in a contaminated paddy field in Tokyo. The cadmium concentrations of irrigated water, open-bulk precipitation, soil solution (leaching water), rice plants collected at the harvesting stage and the chemical fertilizer and the cow manure compost applied were determined. The Cd flux of each factor was calculated by multiplying the Cd concentration by the volume or mass of the media. The annual input-output balance of Cd in the paddy field in 2001 and 2002 was estimated to be -5.44 [corrected] g ha(-1) and -2.01 [corrected] g ha(-1), respectively, indicating the loss of Cd from the paddy field, although the losses accounted for only 0.24% [corrected] and 0.089% [corrected] of the total amount of Cd in the ploughed layer soil in 2001 and 2002, respectively. Among the factors involved, the input from fertilizers (including manure compost) and the output due to the uptake by rice plants played a major role in the balance. The former largely depended on the types and amounts of fertilizers applied, and the latter on the water management practices in the paddy field, such as flooding and drainage of the surface water.     

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.     

A field experiment with variable-suction multi-compartment samplers to measure the spatio-temporal distribution of solute leaching in an agricultural soil

Solutes spread out in time and space as they move downwards from the soil surface with infiltrating water. Solute monitoring in the field is often limited to observations of resident concentrations, while flux concentrations govern the movement of solutes in soils. A recently developed multi-compartment sampler is capable of measuring fluxes at a high spatial resolution with minimal disturbance of the local pressure head field. The objective of this paper is to use this sampler to quantify the spatial and temporal variation of solute leaching below the root zone in an agricultural field under natural rainfall in winter and spring. We placed two samplers at 31 and 25 cm depth in an agricultural field, leaving the soil above undisturbed. Each sampler contained 100 separate cells of 31 × 31 mm. Water fluxes were measured every 5 min for each cell. We monitored leaching of a chloride pulse under natural rainfall by frequently extracting the collected leachate while leaving the samplers buried in situ. This experiment was followed by a dye tracer experiment. This setting yielded information that widely surpassed the information that can be provided by separate anionic and dye tracer trials, and solute transport monitoring by coring or suction cups. The detailed information provided by the samplers showed that percolation at the sampling depth started much faster (approximately 3 h after the start of rainfall) in initially wet soil (pressure head above − 65 cm) than in drier soil (more than 14 h at pressure heads below − 80 cm). At any time, 25% of the drainage passed through 5–6% of the sampled area, reflecting the effect of heterogeneity on the flow paths. The amount of solute carried by individual cells varied over four orders of magnitude. The lateral concentration differences were limited though. This suggests a convective–dispersive regime despite the short vertical travel distance. On the other hand, the dilution index indicates a slight tendency towards stochastic–convective transport at this depth. There was no evidence in the observed drainage patterns and dye stained profiles of significant disturbance of the flow field by the samplers.     

Runoff and leaching of atrazine and alachlor on a sandy soil as affected by application in sprinkler irrigation

Abstract

Rainfall simulation was used with small packed boxes of soil to compare runoff of herbicides applied by conventional spray and injection into sprinkler‐irrigation (chemigation), under severe rainfall conditions. It was hypothesized that the larger water volumes used in chemigation would leach some of the chemicals out of the soil surface rainfall interaction zone, and thus reduce the amounts of herbicides available for runoff. A 47‐mm rain falling in a 2‐hour event 24 hours after application of alachlor (2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxymethyl)‐acetamide) and atrazine (6‐chloro‐N‐ethyl‐N‐(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine) was simulated. The design of the boxes allowed a measurement of pesticide concentrations in splash water throughout the rainfall event. Initial atrazine concentrations exceeding its’ solubility were observed. When the herbicides were applied in 64000 L/ha of water (simulating chemigation in 6.4 mm irrigation water) to the surface of a Tifton loamy sand, subsequent herbicide losses in runoff water were decreased by 90% for atrazine and 91% for alachlor, as compared to losses from applications in typical carrier water volumes of 187 L/ha. However, this difference was not due to an herbicide leaching effect but to a 96% decrease in the amount of runoff from the chemigated plots. Only 0.3 mm of runoff occurred from the chemigated boxes while 7.4 mm runoff occurred from the conventionally‐treated boxes, even though antecedent moisture was higher in the former. Two possible explanations for this unexpected result are (a) increased aggregate stability in the more moist condition, leading to less surface sealing during subsequent rainfall, or (b) a hydrophobic effect in the drier boxes. In the majority of these pans herbicide loss was much less in runoff than in leachate water. Thus, in this soil, application of these herbicides by chemigation would decrease their potential for pollution only in situations where runoff is a greater potential threat than leaching.     

Enhanced transport of pesticides in a field trial with treated sewage sludge

This study was designed to provide high-density data on spatial distribution of three herbicides with different physiochemical characteristics in a sludge-amended and non-amended control field over the course of an irrigation season. The field experiment was carried out on a sandy loam Hamra Red Mediterranean soil (Rhodoxeralf) at Bet Dagan, Israel. After a single 50 mm irrigation event, the mean centers of mass (COM) in the control field were at 15.6, 14.9, and 17 cm for bromacil, atrazine and terbuthylazine, respectively; in the sludge-amended field, mean COMs were at 28.8, 31.2, and 34.1 cm, respectively. After 500 mm of irrigation in the control field, the COM depth distribution of the three pesticides was inversely correlated with octanol-water (Kow) distribution coefficients and soil sorption coefficients (Koc), and positively correlated with aqueous solubilities. After 500 mm irrigation in the sludge-amended field, the mean terbuthylazine COM was at 19.8 cm versus 13.8 cm for the control field, demonstrating a sustained enhanced effect on terbuthylazine transport. Downward transport of atrazine was also enhanced by sludge amendment, albeit less than terbuthylazine. Bromacil was preferentially accumulated in the upper soil layers of the sludge-amended field as compared with the control field after 500 mm irrigation. The enhanced transport of all three pesticides in the sludge-amended field after a single irrigation event is attributed to development of preferential flow pathways around hydrophobic clods of sludge. Enhanced transport of terbuthylazine, and to a lesser extent, atrazine, throughout the irrigation season, is attributed to their transport as complexes with dissolved, colloidal and suspended organic matter derived from sludge degradation.     

Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Leaching of pesticides through normal-tillage and low-tillage soil--a lysimeter study. I. Isoproturon

Isoproturon is a herbicide, which was used in Denmark against grass weeds and broad-leaved weeds until 1998. Isoproturon has frequently been detected in ground water monitoring studies. Leaching of isoproturon (N,N-dimethyl-N'-(4-(1-methylethyl)-phenyl)urea) and its metabolites, N'-(4-isopropylphenyl)-N-methylurea and N'-(4-isopropylphenyl)urea was studied in four lysimetres, two of them being replicates from a low-tillage field (lysimeter 3 and 4), the other two being replicates from a normal tillage field (lysimeter 5 and 6). In both cases the soil was a sandy loam soil with 13-14% clay. The lysimetres had a surface area of 0.5 m2 and a depth of 110 cm. Lysimeter 3 and 4 were sprayed with unlabelled isoproturon while lysimeter 5 and 6 was sprayed with a mixture of 14C-labelled and unlabelled isoproturon. The total amount of isoproturon sprayed onto each lysimeter was 63 mg, corresponding to 1.25 kg active ingredient per ha. The lysimeters were sprayed with isoproturon on October 26, 1997. The lysimetres were installed in an outdoor system in Research Centre Flakkebjerg and were thus exposed to normal climatic conditions of the area. A mean of 360 l drainage water were collected from lysimeter 3 and 4 and a mean of 375 litres from lysimeter 5 and 6. Only negligible amounts of isoproturon and its primary metabolites were found in the drainage water samples, and thus no significant difference between the two lysimeter sets was shown. In a total of 82 drainage water samples, evenly distributed between the four lysimetres isoproturon was found in detectable amounts in two samples and N'-(4-isopropylphenyl)urea was found in detectable amounts in two other samples. The detection limit for all the compounds was 0.02 microg/l. 48% and 54% of the added radioactivity were recovered from the upper 10 cm soil layer in lysimeter 5 and 6, respectively, and 17 and 14% from 10-20 cm's depth. By extraction first with an aquatic CaCl2 solution 0.49% of the added radioactivity was extracted from the upper 10 cm layer in lysimeter 5. In the subsequent extraction with acetonitril, 1.19% of the added radioactivity was extracted. In lysimeter 6, upper 10 cm, 0.2% were extracted with water and 0.56% were extracted with acetonitril. Below 10 cm's depth no measurable amounts could be extracted.     

Estimating the spatial scale of herbicide and soil interactions by nested sampling, hierarchical analysis of variance and residual maximum likelihood

An unbalanced nested sampling design was used to investigate the spatial scale of soil and herbicide interactions at the field scale. A hierarchical analysis of variance based on residual maximum likelihood (REML) was used to analyse the data and provide a first estimate of the variogram. Soil samples were taken at 108 locations at a range of separating distances in a 9 ha field to explore small and medium scale spatial variation. Soil organic matter content, pH, particle size distribution, microbial biomass and the degradation and sorption of the herbicide, isoproturon, were determined for each soil sample. A large proportion of the spatial variation in isoproturon degradation and sorption occurred at sampling intervals less than 60 m, however, the sampling design did not resolve the variation present at scales greater than this. A sampling interval of 20-25 m should ensure that the main spatial structures are identified for isoproturon degradation rate and sorption without too great a loss of information in this field.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.