Rainfastness and adsorption of herbicides on hard surfaces

Herbicides are still used to control weeds on hard surfaces, including municipal, private and industrial sites. Used under unfavourable conditions, especially when rain occurs shortly after application, herbicides may run off to surface waters. Such losses of herbicides from hard surfaces are estimated to be much higher than for herbicides used in arable fields. In this study, three kinds of hard surface were evaluated: asphalt, concrete surface and gravel (fine and coarse). Three herbicides were applied: glyphosate, diuron and diflufenican. Adsorption isotherms of diuron and diflufenican to the three surfaces were determined. At different times after treatment with the herbicides, rainfall was simulated by use of a rain-droplet spray nozzle, and the run-off was collected for analysis. After this run-off event, the materials were immersed in water to measure desorption which, together with the compound in the run-off, gave a measure of the dislodgable residues. The apolar herbicides diuron and especially diflufenican adsorbed strongly to asphalt. The polar herbicide glyphosate lost 75% in run-off from asphalt but was adsorbed strongly to soil and concrete pavement.     

Dissipation of triclopyr herbicide applied in Lake Minnetonka,MN concurrently with Rhodamine WT dye

Fluorescent dye was applied concurrently with triclopyr in two 6.5-ha treatment plots in Lake Minnetonka, MN for data collection to support full aquatic registration of this herbicide. The herbicide and dye mixture was applied by airboat to Phelps Bay with weighted, trailing hoses to maximize uniform distribution of these materials in the water column. A surface application was made to the Carsons Bay plot to attain theoretical triclopyr and dye concentrations of 2500 and 10 micrograms litre-1, respectively. Water samples collected at various times following application showed very little movement of the herbicide and dye out of the Carsons Bay plot. Triclopyr residues moved to a greater extent out of the Phelps Bay plot. The dye was easily tracked in real-time using field fluorometers, which allowed new sampling stations to be established to monitor this movement. Dye concentrations were strongly correlated to herbicide concentrations (r2 = 0.97 in both plots) but were less predictive of the triclopyr metabolite 3,5,6-trichloropyridinol (TCP; r2 = 0.82 in Phelps and r2 = 0.73 in Carsons), probably due to its differential metabolism and degradation. The inert dye can be used to compare the dissipation of herbicide residues by dilution versus microbial or other breakdown processes. Vertical sampling of dye in the water column showed that surface applications of aquatic herbicides can delay uniform mixing in the water column by several days. Although the dye aided the tracking of residues outside the treatment areas, predetermined sampling times and stations were still needed if very low concentrations of herbicide were to be detected at times and stations where the dye had been diluted below its limit of detection.     

Effects of formulation on the run-off of imidacloprid from turf

Imidacloprid is a pesticide often used to control insect pests on residential lawns and golf courses. To investigate its potential to be transported into non-target aquatic systems by rainfall events, imidacloprid was applied as 5.0 g kg-1 GR and 750 g kg-1 WP to 12 plots planted with bermuda grass set on a 5% slope. The dimethylamine salt of the herbicide 2,4-D was applied simultaneously to the plots in order to normalize the results to prior trials conducted with other pesticides. At a rate of 2.5 cm h-1, 5-cm rainfall events were simulated at 24 and 48 h after application and 2.5-cm events were simulated at 96 and 192 h. After each event water was collected from each plot and analyzed by HPLC for residual insecticide or herbicide. Approximately 1.4% of the insecticide formulated as WP and 1.9% of that formulated as GR was lost from the plots after four run-off events. Of the total mass lost, 64% and 30% respectively occurred in the first and second run-off events for the WP formulation versus 75% and 20% for the GR formulation. These values compare with a total mass export of 2.6% for 2,4-D, of which 95% and 4% of the loss occurred respectively in the first and second run-off events. The maximum concentration of imidacloprid detected in run-off water was 0.49 mg litre-1 and occurred during the first run-off event.     

Impacts of tillage and application methods on atrazine and alachlor losses from upland fields

The effects of tillage practises and the methods of chemical application on atrazine and alachlor losses through run-off were evaluated for five treatments: conservation (untilled) and surface (US), disk and surface, plow and surface, disk and preplant-incorporated, and plow and preplant-incorporated treatments. A rainfall simulator was used to create 63.5 mm h⁻¹ of rainfall for 60 min and 127 mm h⁻¹ for 15 min. Rainfall simulation occurred 24–36 h after chemical application. There was no significant difference in the run-off volume among the treatments but the untilled treatment significantly reduced erosion loss. The untilled treatments had the highest herbicide concentration and the disk treatments were higher than the plow treatments. The surface treatments showed a higher concentration than the incorporated treatments. The concentration of herbicides in the water decreased with time. Among the experimental sites, the one with sandy loam soil produced the greatest losses, both in terms of the run-off volume and herbicide loss. The US treatments had the highest loss and the herbicide incorporation treatments had smaller losses through run-off as the residue cover was effective in preventing herbicide losses. Incorporation might be a favorable method of herbicide application to reduce the herbicide losses by run-off.     

Herbicide sorption to concrete and asphalt

In order to accurately predict the fate and behaviour of herbicides following application to hard surfaces, an understanding of the processes involved is required. Previous studies have demonstrated that herbicides with a low soil organic carbon partition coefficient (K(oc)) are preferentially removed from concrete and asphalt surfaces. It is possible, therefore, that sorption may play a role in retaining herbicides to hard surfaces. This study provides an indication of the extent to which herbicides may sorb to concrete and asphalt, and examines the results in the light of other research to identify the significance of sorption in describing herbicide losses after application. There was measurable sorption of herbicides to concrete and asphalt although this was limited compared with that to soils, especially for concrete. An exponential relationship between experimentally derived values of K(p) and literature values of K(oc) for asphalt was established (r(2) = 0.931); there was a weaker relationship for concrete (r(2) = 0.606). The experimentally derived K(p) values could be used to enhance the prediction of herbicide loss to receiving waters following application. It is probable that the fate of herbicides applied to concrete and asphalt surfaces depends more heavily on physical processes than is the case in soils.     

Detection of triazine and urea herbicide residues by various characteristics of oat seedlings in bioassays

Atrazine, simazine, diuron, and linuron applied to soil increased the percentage moisture of oat (Avena sativa L.) shoots in bioassays at the lowest dose tested of 0·25 ppm. Further increases occurred up to 2 ppm but at higher concentrations the percentage moisture decreased. At all doses of each herbicide, shoot dry weight was decreased. In oats grown on soil collected from a peach orchard which had received repeated annual applications of these herbicides, the percentage moisture of the oat shoots was higher than the control value whenever the oat dry weight was decreased and provided a method of residue detection as sensitive as dry weight measurements. Treatment of oats by soil application of the above herbicides in bioassays also caused increases in the electrical conductivity of an aqueous extract of the oat shoots per mg of dry weight and this characteristic was slightly more sensitive than dry weight in detecting herbicides in orchard soil. The conductivity of the extract per mg of water in the shoots, however, only increased as percentage moisture decreased. The weight of neutral water-soluble material in oat shoots decreased much more rapidly than dry weight in bioassays with standard herbicide concentrations. Determination of the weight of neutral water-soluble material in oat plants grown on orchard soil samples indicated the presence of herbicide residues in 50% of the cases in which residues were not detectable by dry weight. The weight of neutral material as a percentage of dry weight was almost as sensitive. Chemical analysis of soil in which oat plants had a decreased level of neutral water-soluble compounds indicated that this characteristic had a lower limit of detection for herbicide residues of approximately 0.10 ppm.     

Surface transport of 2,4-D from small turf plots: observations compared with GLEAMS and PRZM-2 model simulations

A three-year field study was conducted using twelve 7.4×3.7 m plots and simulated rainfall to investigate pesticide run-off following application to a golf course fairway. The plots were sprigged with ‘Tifway 419’ bermudagrass (Cynodon dactylon×C transvaalensis). The dimethylamine salt of 2,4-D [(2,4-dichlorophenoxy)acetic acid] was applied as foliar sprays at a rate of 2.24 kg AI ha⁻¹. Simulated rainfall was applied at an intensity of 29 mm h⁻¹ one day before and 1, 2, 4, and 8 days after the pesticide applications for 0.92, 1.75. 1.75, 0.92, and 0.92 h, respectively. Water run-off was measured using a tipping-bucket apparatus and sub-samples were analyzed for pesticide residues. Data collected from the study were also compared with the GLEAMS and PRZM-2 model simulations for surface water and 2,4-D run-off. Mass and concentration of 2,4-D in run-off decreased rapidly, with 74.5% of the total run-off of 2,4-D occurring in the first run-off event after treatment. When calibrated to the site-specific characteristics, the GLEAMS and the PRZM-2 models adequately simulated the average of surface water run-off over all plots, with normalized root mean square error (NRMSE) and coefficient of determination for linear regression (R²) being 22.8% and 0.917 for GLEAMS, and 23.7% and 0.879 for PRZM-2, respectively. However, both GLEAMS (NRMSE=82.1%, R²=0.776) and PRZM-2 (NRMSE=125.8%, R²=0.513) less accurately simulated 2,4-D concentrations in run-off. © 1999 Society of Chemical Industry     

Survey of herbicide residues in soil and wells in three citrus orchards in Valencia, Spain

Soil samples taken in summer 1989 and winter 1990 at different depths from three citrus orchards of the Valencia region (Spain) with a long history of residual herbicide treatments were analysed with bioassays and chromatographic procedures. The herbicides involved were atrazine, bromacil, diuron, simazine, terbuthylazine, terbumetone, terbutryn and trifluralin. Water samples from wells in the orchards were also analysed. The concentrations of the herbicides were very low, often below the limit of determination, and were always highest in the upper layers of soil. After a very unusual period of heavy rain, small quantities of some chemicals were found in the well water. The conclusion was that in these orchards the herbicides applied at currently used rates are unlikely to accumulate in any layers of the soil.     

Sorption and leaching potential of herbicides on Brazilian soils

Sorption of the herbicides alachlor, atrazine, dicamba, hexazinone, imazethapyr, metsulfuron-methyl, nicosulfuron, simazine and sulfometuron-methyl was characterized on six Brazilian soils, using the batch equilibration method. In general, weak acid herbicides (dicamba, imazethapyr, metsulfuron-methyl, nicosulfuron and sulfometuron-methyl) were the least sorbed, whereas weak bases such as triazines and nonionic herbicides (alachlor) were the most sorbed. The Kd values found showed a significant correlation with soil organic carbon content (OC) for all herbicides except imazethapyr and nicosulfuron. Koc values showed a smaller variation among soils than Kd . To estimate the leaching potential, Koc and the ground-water ubiquity score (GUS) were used to calculate half-lives ( t_1/2 ) that would rank these herbicides as leachers or non-leachers. Comparison of calculated values to published values for t_1/2 demonstrated that sulfonylureas and hexazinone are leachers in all soils, alachlor is transitional, and atrazine, simazine and dicamba are leachers or transitional, depending on soil type. Results discussed in this paper provide background to prioritize herbicides or chemical groups that should be evaluated in field conditions with regard to their leaching potential to ground-water in tropical soils.     

Influence of topsoil tilth and soil moisture status on losses of pesticide to drains from a heavy clay soil

Twelve lysimeters with a surface area of 0.5 m² and a length of 60 cm were taken over mole drains from a Denchworth heavy clay soil and divided into two groups with either a standard agricultural tilth or a finer topsoil tilth. The influence of topsoil tilth on leaching of the herbicide isoproturon and a bromide tracer was evaluated over a winter season. The effect of variations in soil moisture status in the immediate topsoil on leaching of isoproturon, chlorotoluron and linuron was investigated in the following winter season. Here, water inputs were controlled such that lysimeters received 50 mm at a maximum intensity of 2 mm h^?1 over a 4‐week period with herbicides applied on day 15. Three treatments received the water either all prior to application, all after application, or evenly spread over the 4‐week period. Leaching losses of the three herbicides were monitored for a subsequent drainage event. Analysis of covariance showed a significant effect of topsoil tilth and total flow on both the maximum concentrations (P = 0.034) and total losses (P = 0.012) of isoproturon in drainflow. Both concentrations and losses were c 35% smaller from lysimeters with the finer tilth. However, generation of the fine tilth in the field was restricted by a wet autumn and this is not considered a reliable management option for reducing pesticide losses from heavy clay soils. In the second experiment, variation in soil moisture content prior to and after application did not have any significant effect (P < 0.05) upon subsequent losses of the three herbicides to drains. © 2001 Society of Chemical Industry     

Larvicidal activity against Plutella xylostella of cordycepin from the fruiting body of Cordyceps militaris

The insecticidal activities of methanol extracts of Cordyceps militaris Link (Ascomycotina: Clavicipitaceae) cultured on fresh pupae of Bombyx mori L against 3rd-instar larvae of Plutella xylostella L were examined using direct contact application. The larvicidal activity was more pronounced in an extract of C militaris fruiting body than in an extract of the pupae separated from the culture. The biologically active constituent of the Cordyceps fruiting body was characterized as cordycepin (3'-deoxyadenosine) by spectroscopic analysis. Responses varied according to dose, exposure time and application method. In a leaf-dipping test, cordycepin at 500 mg litre-1 caused no mortality at 1 DAT (day after treatment) but 78 and 100% mortality at 2 and 4 DAT, respectively, whereas 34 and 88% mortality at 3 and 5 DAT, respectively was observed at 300 mg litre-1. Cordycepin caused body colour change from pale green to dark brown and eventually body lysis. These results suggested that the larvicidal action may be attributable to a direct effect rather than an inhibitory action on chitin synthesis. There was a significant difference in insecticidal activity of cordycepin between leaf dipping (500 mg litre-1) with 100% mortality and topical application (10 micrograms per larva) with 0% mortality, suggesting that cordycepin has stomach action. Cordycepin merits further study as a potential P xylostella control agent or as a lead compound.     

4-取代嘧啶基苯磺酰脲类化合物的合成与除草活性

为了探寻磺酰脲类除草剂的构效关系,以单嘧磺隆和单嘧磺酯为先导化合物,在嘧啶环上引入取代苯基,设计合成了16个新型单取代嘧啶磺酰脲衍生物,其结构均经过核磁共振氢谱、质谱和元素分析确证。盆栽试验结果表明:在1.5 kg/hm2时,大部分化合物对供试杂草具有一定的抑制活性,其中对双子叶杂草的活性高于对单子叶杂草的活性,但均不及先导化合物的活性。     

Herbicide loss following application to a railway

Railways have been identified as a potential source of herbicides detected in surface and groundwaters, but there are few data to support this theory. Two studies were undertaken to investigate the fate of herbicides applied to railway trackbeds: a pilot study in a section of a disused, but intact, cutting where runoff and throughflow were sampled from trenches adjacent to the treated area, and a larger scale study on 0.75 km of embankment where surface water from the drainage ditch at the base of the embankment and groundwater were sampled. In the pilot study, peak concentrations of atrazine, diuron and glyphosate (1280, 210 and 15 microg litre(-1) respectively) were detected 6days after treatment (DAT). Oxadiazon, oryzalin and isoxaben were not detected above their limits of quantification. Lower concentrations were detected 81 DAT (10 and 0.8 microg litre(-1) of atrazine and glyphosate respectively). In the larger scale study, herbicides were not detected, in either the surface water or groundwater, at concentrations above the limit of detection that could be attributed to application to the railway. Rainfall volume and depth to sampling point may partly explain the different results obtained from the two studies. The findings are compared with herbicide losses from other 'hard surfaces'.     

Studies on a new group of biodegradable surfactants for glyphosate

The effectiveness of a homologous series of biodegradable rapeseed oil derivatives (triglyceride ethoxylates; Agnique RSO series containing an average of 5, 10, 30 and 60 units of ethylene oxide (EO) as adjuvants for foliage-applied, water-soluble, systemic active ingredients was evaluated employing glyphosate as an example. Previous experiments had revealed that the surfactants used are not phytotoxic at concentrations ranging from 1 to 10 g litre-1. The experiments were performed using Phaseolus vulgaris L and nine selected weed species, grown in a growth chamber at 25/20 (+/- 2) degrees C day/night temperature and 40/70 (+/- 10)% relative humidity. The surfactants were evaluated for enhancement of spray retention, and foliar penetration biological efficacy of glyphosate. Glyphosate was applied at a concentration of 43 mM. The surfactants were added at concentrations of 1 g litre-1. The commercial glyphosate 360 g AE litre-1 SL Roundup Ultra and unformulated glyphosate served as references. The surfactants used improved spray retention, foliar penetration and biological efficacy. Some of the formulations were comparable to the performance of Roundup Ultra in the aspects evaluated; some were even more effective in enhancing spray liquid retention and promoting glyphosate phytotoxicity in several plant species. In these studies Agnique RSO 60 generally was most effective.     

Field experiments to investigate long-term effects of repeated applications of MCPA, tri-allate, simazine and linuron: II. Crop performance and residues 1969–78

In four field experiments begun in 1963, each of four herbicides was applied to plots planted wilh the same crop each year. The annual treatments were: MCPA at 17 kg/ha to barley (Hordeum sativa Jess) and wheat (Triticum aestivum L.) at growth stage 15. tri-allate at 17 kg/ha pre-emergcnce to barley and wheat, simazine at l7kg/ha pre-emergence to maize (Zea mays L.) and linuron in two applications of 084 kg/ha pre- and post-emergence to carrots (Daucus carota L.). MCPA did not affect growth or yield of either barley or wheat. In general tri-allate also did not aftect the crops although wheat yield was depressed in 1978, wheat 1000 grain weight was reduced in 1972 and barley germination percentage was increased in 1973. Simazine did not influence the height, yield or appearance of maize. Linuron normally produced no effect on carrot yield, density and size. However, in 2 years when the post-emergence application was late, density but not yield was lower than in control plots. There was no accumulation of residues of any of these compounds in the soil. Rates of loss were similar to those predicted on ihe basis of laboratory experiments. In a fifth experiment these herbicides were applied twice per year (3 times in the case of linuron) at double the rales above on each occasion to bare plots. These applications ceased in 1968 (1969 for MCPA) but residues were monitored until 1972 except in the case of MCPA. Disappearance rates were similar to those in the cropped plots and residues were largely confined to the top 10 cm. The plots treated with MCPA had developed an enhanced ability lo degrade il prior to 1968. This persisted for 5 years after the final application.     

Contribution of non-agricultural pesticides to pesticide load in surface water

Two small creeks, tributaries of the River Ruhr near Schwerte, Federal Republic of Germany, were investigated to reveal the regional agricultural and non-agricultural sources of pesticide inputs and the main pathways to surface water. In addition, the receiving water was monitored for pesticides. The watersheds are situated at the northern margin of the Rhenian Schiefergebirge, a highland landscape in North-Rhine-Westphalia. Solid carboniferous shale is covered by a shallow layer of quaternary unconsolidated rock (porous aquifer thickness <5 m). Occurrence of herbicides such as chlortoluron, isoproturon and terbuthylazine in surface water could be due to their broad agricultural application in regional dominant crops, such as barley, wheat and maize. Occurrence of diuron and glyphosate results from their use in residential settlements and industrial areas as well as from weed control on railway tracks. Atrazine concentrations up to 0.8 microg litre(-1) indicated recent use of this herbicide, which has been banned since 1991, and was also the result of non-agricultural applications. Pathways for pesticide input to the receiving waters were related to both surface run-off and underground passage. Two-thirds of the observed diuron load in the surface water resulted from an input by run-off. This was expected as a result of total herbicide application targets to sealed surfaces infringing current regulations and recommendations. Diuron load varied between 0.6 and 1.2% of the estimated amount applied annually in the investigated catchments. Non-agricultural pesticide use contributed more than two-thirds of the whole observed pesticide load in the tributaries and at least one-third in the River Ruhr.     

Movement of pendimethalin,ioxynil and soil particles to field drainage tiles

Knowledge of the movement of herbicides and soil particles to sub-surface tile drainage may help to predict chemical leaching to surface waters and deeper groundwater systems. The movement of pendimethalin (2 years), ioxynil (1 year) and soil particles (3 years) to two tile drains was investigated on a sandy loam soil under natural weather conditions. Herbicide and particle concentrations in the drain water showed a very dynamic pattern. The largest herbicide concentrations were detected during the first tile drain flow events after application. Very little herbicide was lost with drain water later than 2 months after application. The turbidity, reflecting concentrations of soil particles, correlated positively and strongly with the pendimethalin concentration and negatively with the rate of drain water discharge, whereas it was uncorrelated with the ioxynil concentration. Peak turbidity values occurred during or shortly after rainfall events, either in break of frost situations, or on unfrozen soil coinciding with the occurrence of peak moisture contents in the topsoil well (3-7%) above field capacity. On average, 0.0013% of the applied pendimethalin and 0.0015% of the applied ioxynil were lost with drain water. The results suggest that preferential flow promotes the movement of all three substances to the tile drains but indicate somewhat different transport mechanisms for the two herbicides.     

Enhanced degradation of iprodione and vinclozolin in soil

Residues of iprodione and vinclozolin were measured following repeated application of the fungicides to a sandy loam soil in the laboratory. There was a progressive increase in rates of degradation with successive treatments. With iprodione, for example, the times for 50% loss of the first and second applications were about 23 and 5 days respectively. When treated for the third time, less than 10% of the applied dose remained in the soil after just 2 days. Similar results were obtained with vinclozolin in the same soil, and with both compounds in a second soil. In a third soil, which had relatively low pH, degradation of both compounds occurred only slowly and the rate of degradation of a second application was the same as that of the first. Degradation rates in this soil were increased by addition of 100 g kg^?1 of a soil in which degradation occurred more readily, and they were markedly increased by addition of 100 g kg^?1 of a soil in which enhanced degradation had been previously induced. Residues of both fungicides were also measured following repeated application in the field. When iprodione was applied to previously untreated plots, about 3% of the initial dose remained in the soil after 77 days. When applied to plots treated once before, less than 1% remained after 18 days, and when applied to plots treated twice previously less than 1% remained after 10 days. Similar results were obtained with vinclozolin. Enhanced degradation of subsequent soil treatments was also observed following a sequence of low-dosage sprays in the field.     

The effects of temperature, humidity and rainfall on captan decline on apple leaves and fruit in controlled environment conditions

BACKGROUND: Captan is an important fungicide for controlling diseases in horticultural crops. Predicting its dissipation is important for estimating dietary risks and optimising pesticide application. Experiments were conducted to determine the relationship of captan loss on apple leaves with temperature, humidity and rainfall, and to investigate captan loss on fruit in dry conditions. RESULTS: There was large unit-to-unit variability in captan residues in spite of the controlled application. Temperature and humidity had negligible effects on captan loss. Captan loss is predominately due to washoff by rain, although a certain proportion of captan may bind to the plant surface tightly and hence may not be readily removed by rain. About 50% of captan can be washed off by as little as 1 mm of rain after an application, and the loss appeared not to relate to the amount of rain. Under dry conditions, daily loss of captan is estimated to be around 1% on both fruit and leaves, giving a half-life of ca 70 days. CONCLUSIONS: Captan loss on leaf and fruit surfaces is primarily due to rain washoff.     

Rice paddy field herbicides and their effects on the environment and ecosystems

Paddy herbicides contribute to the reduction of weeding labor, however, there are concerns about their effects on the environment and ecosystems. The environmental burden of applied herbicides is heaviest in water systems such as irrigation channels and rivers. Herbicides are generally detected in rivers in concentrations in levels of ng/L for only 2 to 3 months after use. It is to be regretted that herbicides have been implicated in accidents involving fish, the impeded propagation of algae and other non‐target organisms. Therefore, it is necessary to assess the ecological risk, and the Environment Agency in Japan compiled an interim report on how pesticides' ecological effects should be assessed. Pesticides are separately examined for their toxicity (hazard assessment) and exposure (exposure analysis). However, to the environment and ecosystems there are many problems in assessing the ecological risk of pesticides, such as selection of geographic locations, methodology of assessing the impacts on ecosystems and monitoring the effect of pesticides. New herbicides are expected to have high selectivity and low toxicity. Decreasing herbicide toxicity requires high selectivity to distinguish target weeds from crops and non‐target organisms. New groups of compounds will be developed based on a biorational approach. Moreover, it is necessary to develop an environmentally low‐impact application method such as the use of granular types and sustained‐release formulation among others. It is important that integrated methods be used to control paddy weeds by combining ecological/agronomical, mechanical and biological control methods, instead of relying solely on chemical herbicides.