Persistence and runoff losses of 3 herbicides and chlorpyrifos from a corn field in the Lake Balaton watershed of Hungary

Corn is intensively cultivated in western Hungary in the basin of Lake Balaton, one of the most important water resources in eastern Europe. Pesticide runoff was measured in 1996 and 1997 from a typical corn field near Zalaegerszeg, Hungary, which drains into the Zala River, an important water source of Lake Balaton. Three herbicides, namely atrazine, acetochlor, and propizochlor, and the insecticide chlorpyrifos were applied to bare soil in a field with 5% slope and soil and runoff water pesticide concentrations were monitored. In 1997, a rainfall-runoff simulation experiment was conducted on a small sub-plot in order to measure pesticide runoff under reasonable worst-case conditions. Under natural rainfall almost all losses occurred in a large runoff event in 1996 one month after application in which 3% of atrazine and 1% of acetochlor was transported off the field. Propizochlor and chlorpyrifos losses in the same event were much lower: 0.2% and <0.01%, respectively, because of these chemicals' shorter persistence times in near-surface soil. The rainfall simulation produced only trace amounts of losses even though 4.1 cm was applied in 2 hours; the soil was extremely dry and only 0.2 cm runoff occurred containing less than 0.01% of all chemicals applied. The results suggest that intensive use of corn herbicides, which have been found to result in widespread contamination of water resources elsewhere, may be expected to have the same impact in the Balaton watershed depending on the amounts and intensities used in the basin.     

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.     

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.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (Kf values) generally decreased in the order: soybean-fed > corn-fed > not-fed-earthworm-castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (Koc values) was significantly greater for corn-castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean- and corn-castings treatments was always less than desorption from soil and not-fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Atrazine and metolachlor residues in brookston Cl following conventional and conservation tillage culture

Atrazine and metolachlor are extensively used in Ontario, Canada for control of broadleaf weeds and annual grasses in corn. Conservation tillage may alter the physical and biological environment of soil affecting herbicide dissipation. The rate of dissipation of these two herbicides in soil from conventional, ridge and no-tillage culture was followed. Herbicide dissipation was best described by first order reaction kinetics. Half life, the time for herbicide residues to dissipate to half their initial concentration, was unaffected by tillage. Half life for atrazine and metolachlor was similar and ranged from 31 to 66 d. The rate of dissipation decreased in dry years when soil moisture content was low. In a dry year, herbicide residues during the growing season were significantly greater on ridge tops than in the other tillage treatments. However, after harvest no differences in herbicide residues were detected among tillage treatments. Residues of atrazine (6 to 9% of applied) and metolachlor (4 to 6%) were detected in soil before planting a year after application. De-ethyl atrazine, the primary degradation product of atrazine, increased in concentration during the growing season with the greatest concentrations measured at harvest and in years when atrazine dissipated fastest. De-ethyl atrazine one year after application accounted for about 12% of the remaining triazine residue. These herbicide residues would not be phytotoxic to subsequent crops but are a potential source for leaching to ground and surface waters.     

Runoff of trifluralin,metolachlor, and metribuzin from a clay loam soil of Louisiana

Trifluralin[2,6-dinitro-N,N-dipropyl-4-(trifluormethyl)benzenamine], metolachlor[2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] and metribuzin[4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)one] were applied as pre-emergent herbicides to soybean plots in Louisiana (LA) at the rate of 1683 g/ha, 2759 g/ha and 609 g/ha, respectively. The concentrations of trifluralin in the runoff water ranged between 0.09 ng/mL and 0.02 ng/mL, which is lower than the 2 ng/mL US Environmental Protection Agency (EPA) advisory level for trifuralin in drinking water. Metolachlor concentrations in the runoff water ranged from 9.0 ng/mL to 221.5 ng/mL, which is both lower and higher than the 175 ng/mL EPA advisory level for metolachlor. Similarly, metribuzin concentrations in the runoff water ranged between 1.5 ng/mL and 56.2 ng/mL, which is also lower and higher than the 10 ng/mL EPA advisory level for metribuzin. Accordingly, from the field plots located on a Commerce clay loam soil in LA, although the concentration of trifluralin in runoff water were substantially lower than the EPA advisory level, metolachlor and metribuzin concentrations are likely to exceed the EPA advisory levels early on in the application season with a subsequent rapid decrease to safe levels. The total loss of trifluralin in runoff water was 0.005% of the applied amount over an 89 day period after application. The total loss of metolachlor and metribuzin in the runoff water was 4.67% and 5.36% of the applied amount, respectively, over a 22 day period after application. As such, there was almost no movement of trifluralin in the runoff water, whereas metolachlor and metribuzin were much more easily moved.     

Sorption of atrazine and metolachlor by burrow linings developed in soils with different crop residues at the surface

Atrazine and metolachlor sorption by earthworm (Lumbricus terrestris L.) burrows was measured by introducing herbicides into the burrows and collecting the effluent between 0 to 3, 3 to 6, and 6 to 9 min of simulated burrow flow. On average, sorption by burrow linings reduced the herbicide concentration to 78% (atrazine) and 74% (metolachlor) of the applied herbicide solution concentration. For both herbicides, the amount sorbed was dependent on the food source available to the earthworm, as well as the duration of burrow flow. On average, soybean-fed- and corn-fed-earthworm-burrows significantly retained more herbicides relative to the Control Treatment (unfed-earthworms). More herbicides were transported through the burrows with time because the lateral flow movement from the burrow wall into the soil matrix decreased. It is also likely that herbicides retained on burrow linings during the first 3 min of flow saturated the adsorption sites on the burrow wall, which decreased the subsequent retention potential of herbicides in flow between 3 to 9 min. Based on these results, we conclude that herbicide transport through earthworm burrows in the field will be related to crop and crop residue management practices.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Abstract

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (K_f values) generally decreased in the order: soybean‐fed > corn‐fed > not‐fed‐earthworm‐castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (K_oc values) was significantly greater for corn‐castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean‐ and corn‐castings treatments was always less than desorption from soil and not‐fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Effect of buffer strips and soil texture on runoff losses of flufenacet and isoxaflutole from maize fields

The influence of buffer strips and soil texture on runoff of flufenacet and isoxaflutole was studied for two years in Northern Italy. The efficacy of buffer strips was evaluated on six plots characterized by different soil textures; two plots had Riva soil (18.6% sand, 63.1% silt, 18.3% clay) while the remaining four plots had Tetto Frati (TF) soil (37.1% sand, 57% silt, 5.9% clay). Additionally, the width of the buffer strips, constituted of spontaneous vegetation grown after crop sowing, was also compared for their ability to abate runoff waters. Chemical residues in water following runoff events were investigated, as well as their dissipation in the soil. After the first runoff events, concentrations of herbicides in water samples collected from Riva plots were as much as four times lower in waters from TF plots. On average of two growing seasons, the field half-life of flufenacet in the upper soil layer (5 cm) ranged between 8.1 and 12.8 days in Riva soil, 8.5 and 9.3 days in TF soil. Isoxaflutole field half-life was less than 1 day. The buffer strip was very affective by the uniformity of the vegetative cover, particularly, at the beginning of the season. In TF plots, concentration differences were generally due to the presence or absence of the buffer strip, regardless of its width.     

Pendimethalin and oxyfluorfen degradation under two irrigation conditions over four years application

A four-year field study was conducted to determine the effect of pluviometric conditions on pendimethalin and oxyfluorfen soil dynamics. Adsorption, dissipation and soil movement were studied in a sandy loam soil from 2003 to 2007. Pendimethalin and oxyfluorfen were applied every year on August at 1.33 and 0.75 kg ha^?1, respectively. Herbicide soil concentrations were determined at 0, 10, 20, 40, 90 and 340 days after application (DAA), under two pluviometric regimens, natural rainfall and irrigated (30 mm every 15 days during the first 90 DAA). More than 74% of the herbicide applied was detected at the top 2.5 cm layer for both herbicides, and none was detected at 10 cm or deeper. Pendimethalin soil half-life ranged from 10.5 to 31.5 days, and was affected mainly by the time interval between application and the first rain event. Pendimethalin soil residues at 90 DAA fluctuated from 2.5 to 13.8% of the initial amount applied, and it decreased to 2.4 and 8.6% at 340 DAA. Oxyfluorfen was more persistent than pendimethalin as indicated by its soil half-life which ranged from 34.3 to 52.3 days, affected primarily by the rain amount at the first rainfall after application. Oxyfluorfen soil residues at 90 DAA ranged from 16.7 to 34.8% and it decreased to 3.3 and 17.9% at 340 DAA. Based on half-life values, herbicide soil residues after one year, and soil depth reached by the herbicides, we conclude that both herbicides should be considered as low risk to contaminate groundwater. However, herbicide concentration at the top 2.5 cm layer should be considered in cases where runoff or soil erosion could occur, because of the potential for surface water contamination.     

Persistence of seven pesticides as influenced by soil moisture1

Abstract

Pesticides are often applied in combination, but less‐often is soil persistence measured this way. The present field and laboratory study determined relative persistence of five herbicides and two insecticides, co‐applied, as a function of three soil water contents. Losses were modeled adequately by first‐order dissipation, with no significant improvement by using a two‐compartment model. The order of persistence in a silt loam, at 25% moisture, was carbofuran < cyanazine < metribuzin = alachlor < atrazine < ethoprop < metolachlor (t_½ ranged from 7–91 days). Carbofuran degradation increased greatly from 12–25% soil moisture; atrazine was unaffected by 12–35%, whereas the remaining compounds showed limited increasing loss in wetter soil. Field‐based persistence was more variable, but generally similar to lab rankings.     

Quantification of runoff in laboratory-scale chambers

Many of the variables that control transport of agrochemicals and pathogens in the field are difficult to measure because parameters such as slope, soil and plant conditions, and rainfall cannot be adequately controlled in the natural environment. This paper describes the design, construction, operation and performance of a system useful for studying surface transport of agrochemicals and pathogens under controlled slope, rainfall and soil conditions. A turntable is used to support and rotate 4 soil chambers under oscillating dripper units capable of simulating rainfall intensities from 1 to 43 mm h-1. Chambers (35 x 100 x 18 cm i.d.) were constructed with an adjustable height discharge gate to collect runoff and three drains to collect leachate. Height adjustable platforms were constructed to support and elevate the chambers up to 20% slope. The chambers were uniformly packed with 35 to 45 kg of soil (bulk density 1.18-1.27 g cm-3) and initially saturated with two low intensity rain events. The coefficient of variation of the rainfall delivery over a range of 5 to 43 mm h-1 averaged 7.5%. An experiment to determine the variability between chambers in runoff amount and uniformity indicated that at least one runoff-equilibration cycle is needed to obtain steady state conditions for conducting runoff transport evaluations. Another experiment conducted to evaluate atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] runoff under simulated crop-residue covered vs bare soil conditions indicated six times more runoff from bare than crop residue covered soil. The system is capable of precise application of simulated rain, the simultaneous collection of runoff and leachate at slopes up to 20% and can be easily modified to meet a wide range of research parameters.     

Leaching and degradation of corn and soybean pesticides in an Oxisol of the Brazilian Cerrados

Pesticide pollution of ground and surface water is of growing concern in tropical countries. The objective of this pilot study was to evaluate the leaching potential of eight pesticides in a Brazilian Oxisol. In a field experiment near Cuiabá, Mato Grosso, atrazine, chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, metolachlor, monocrotofos, simazine, and trifluraline were applied onto a Typic Haplustox. Dissipation in the topsoil, mobility within the soil profile and leaching of pesticides were studied for a period of 28 days after application. The dissipation half-life of pesticides in the topsoil ranged from 0.9 to 14 d for trifluraline and metolachlor, respectively. Dissipation curves were described by exponential functions for polar pesticides (atrazine, metolachlor, monocrotofos, simazine) and bi-exponential ones for apolar substances (chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, trifluraline). Atrazine, simazine and metolachlor were moderately leached beyond 15 cm soil depth, whereas all other compounds remained within the top 15 cm of the soil. In lysimeter percolates (at 35 cm soil depth), 0.8-2.0% of the applied amounts of atrazine, simazine, and metolachlor were measured within 28 days after application. Of the other compounds less than 0.03% of the applied amounts was detected in the soil water percolates. The relative contamination potentials of pesticides, according to the lysimeter study, were ranked as follows: metolachlor > atrazine = simazine > monocrotofos > endsulfane alpha > chlorpyrifos > trifluraline > lambda-cyhalothrin. This order of the pesticides was also achieved by ranking them according to their effective sorption coefficient Ke, which is the ratio of Koc to field-dissipation half-life.     

On-farm bioremediation of dimethazone and trifluralin residues in runoff water from an agricultural field

Bioremediation is the use of living organisms, primarily microorganisms, to degrade environmental contaminants into less toxic forms. Nine biobeds (ground cavity filled with a mixture of composted organic matter, topsoil, and a surface grass) were established at Kentucky State University research farm (Franklin County, KY) to study the impact of this practice on reducing surface runoff water contamination by residues of dimethazone and trifluralin herbicides arising from an agricultural field. Biobed (biofilter) systems were installed at the bottom of the slope of specially designed runoff plots to examine herbicides retention and degradation before entering streams and rivers. In addition to biobed systems, three soil management practices: municipal sewage sludge (SS), SS mixed with yard waste compost (SS + YW), and no-mulch rototilled bare soil (NM used for comparison purposes) were used to monitor the impact of soil amendments on herbicide residues in soil following natural rainfall events. Organic amendments increased soil organic matter content and herbicide residues retained in soil following rainfall events. Biobeds installed in NM soil reduced dimethazone and trifluralin by 84 and 82%, respectively in runoff water that would have been transported down the land slope of agricultural fields and contaminated natural water resources. Biobeds installed in SS and SS+YW treatments reduced dimethazone by 65 and 46% and trifluralin by 52 and 79%, respectively. These findings indicated that biobeds are effective for treating dimethazone and trifluralin residues in runoff water.     

Dissipation of terbuthylazine,metolachlor, and mesotrione in soils with contrasting texture

ABSTRACT

This study evaluates the dissipation of terbuthylazine, metolachlor, and mesotrione at different depths in soils with contrasting texture. The field trial was conducted at the Padua University Experimental Farm, north-east Italy. The persistence of three herbicides was studied in three different soil textures (clay soil, sandy soil, and loamy soil) at two depths (0–5 and 5–15 cm). Soil organic carbon content was highest in the clay (1.10%) followed by loam (0.67%) and sandy soil (0.24%); the pH of soils was sub-alkaline. Terbuthylazine, metolachlor, and mesotrione were applied on maize as a formulated product (Lumax®) at a dose of 3.5 L ha^?1. Their dissipation in the treated plots was followed for 2 months after application. The concentrations of herbicides were analyzed by liquid chromatography-mass spectrometry. The dissipation of terbuthylazine, metolachlor, and mesotrione could be described by a pseudo first-order kinetics. Terbuthylazine showed the highest DT50, followed by metolachlor and mesotrione. Considering the tested soil, the highest DT50 value was found in clay soil for terbuthylazine and metolachlor, whereas for mesotrione there was no difference among soils. Significant differences were found between the two soil depths for terbuthylazine and metolachlor, whereas none were found for mesotrione. These results suggest that soil texture and depth have a strong influence on the dissipation of terbuthylazine and metolachlor, whereas no influence was observed on mesotrione because of its chemical and physical properties.     

Effect of vegetative filter strips on herbicide runoff under various types of rainfall

Narrow vegetative filter strips proved to effectively reduce herbicide runoff from cultivated fields mainly due to the ability of vegetation to delay surface runoff, promote infiltration and adsorb herbicides. A field trial was conducted from 2007 to 2009 in north-east Italy in order to evaluate the effectiveness of various types of vegetative filter strips to reduce spring-summer runoff of the herbicides mesotrione, metolachlor and terbuthylazine, widely used in maize, and to evaluate the effect of the rainfall characteristics on the runoff volume and concentration. Results show that without vegetative filter strip the herbicide load that reaches the surface water is about 5-6 g ha⁻¹ year⁻¹ for metolachlor and terbuthylazine (i.e. 0.5-0.9% of the applied rate), confirming that runoff from flat fields as in the Po Valley can have a minor effect on the water quality, and that most of the risk is posed by a few, or even just one extreme rainfall event with a return period of about 25-27 years, causing runoff with a maximum concentration of 64-77 μg L⁻¹. Mesotrione instead showed rapid soil disappearance and was observed at a concentration of 1.0-3.8 μg L⁻¹ only after one extreme (artificial) rainfall. Vegetative filter strips of any type are generally effective and can reduce herbicide runoff by 80-88%. Their effectiveness is steady even under severe rainfall conditions, and this supports their implementation in an environmental regulatory scheme at a catchment or regional scale.     

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.     

Effect of a full-grown vegetative filter strip on herbicide runoff: maintaining of filter capacity over time

Narrow vegetative filter strips (VFS) proved to effectively reduce herbicide runoff from cultivated fields mainly due to the ability of vegetation to delay surface runoff, promote infiltration and adsorb herbicides. Since VFS are dynamic systems, their performance would not remain constant over the years indicating the need to define suitable buffer management. In order to evaluate the performance of different five and six year-old VFS, the runoff of the herbicides metolachlor and terbuthylazine was monitored in 2002 and 2003 in an experimental site in northern Italy. The structure of the herbaceous cover in the buffers changes over time. When rows of trees are present, the grass cover is decreased by the shading action of the trees, but the leaf litter gains importance. In VFS with grass cover only, the cover composition changes because of the substitution of grass by broadleaf species. Six metres wide VFS are very effective in reducing runoff volume and concentration during both wet and dry years. Classification analysis showed that runoff concentration and volume are linked to the characteristics of the rainfall event, buffer, source of herbicides and time after application. Regression analysis showed that the significant predictors for runoff volume are rainfall amount and intensity, total vegetal cover in the VFS, crop leaf area index and time after treatment; for concentration they are rainfall intensity, crop leaf area index and total vegetal cover in the VFS. The role of VFS is complex, so appropriate management is required to maintain its increasing filtering capacity over time.     

Calibration and field application of a solvent-based cellulose membrane passive sampling device for the monitoring of polar herbicides

A passive sampler device selective for hydrophilic analytes was constructed from cellulose membrane (40microm thickness) pre-stained with ruthenium red for 96-168h to impede degradation of the cellulose. The sampling device consisted of pre-stained cellulose membrane tubing containing a binary mixture of the solvents 1-dodecanol and 2,2,4-trimethylpentane as the sequestering medium. A laboratory flow-through system was used to investigate the rates of uptake of herbicides into the solvent mixture of the device and their release. The target herbicides were diuron, atrazine, metolachlor and molinate. Uptake of the herbicides into the solvent mixture of the cellulose membrane device was linear for up to 22 days, and daily sampling rates were determined. Release half-lives from the solvent mixture of the sampling device varied from 14 days for diuron, 15 days for atrazine, 84 days for metolachlor and 28 days for molinate. A field study was undertaken to determine if herbicide concentrations in agricultural drainage water derived from the passive sampler devices deployed for periods from 7 to 22 days, using the laboratory-derived sampling rates, would compare closely with time-weighted average herbicide concentrations determined from extractions of daily composite water samples. The concentrations of diuron, atrazine, metolachlor and molinate determined using the cellulose membrane devices were within twofold of the cumulated mean of the daily drainage water extractions.     

Biotransformation of atrazine and metolachlor within soil profile and changes in microbial communities

Biotransformation studies of atrazine, metolachlor and evolution of their metabolites were carried out in soils and subsoils of Northern Greece. Trace atrazine, its metabolites and metolachlor residues were detected in field soil samples 1 year after their application. The biotransformation rates of atrazine were higher in soils and subsoils of field previously exposed to atrazine (maize field sites) than in respective layers of the field margin. The DT₅₀ values of atrazine ranged from 5 to 18 d in the surface layers of the adapted soils. DT₅₀ values of atrazine increased as the soil depth increased reaching the value of 43 d in the 80-110 cm depth layer of adapted soils. Metolachlor degraded at slower rates than atrazine in surface soils, subsoils of field and field margins with the respective DT₅₀ values ranging from 56 to 72 d in surface soils and from 165 to 186 d in subsoils. Hydroxyatrazine was the most frequently detected metabolite of atrazine. The maximum concentrations of metolachlor-OXA and metolachlor-ESA were detected in the soil layers of 20-40 cm depth after 90 d of incubation. Principal Component Analysis (PCA) of soil Phospholipid Fatty Acids (PLFAs), fungal/bacterial and Gram-negative/Gram-positive ratios of the PLFA profiles revealed that the higher biotransformation rates of atrazine were simultaneously observed with the abundance of Gram-negative bacteria while the respective rates of metolachlor were observed in soil samples with abundance of fungi.