Adsorption and degradation of four acidic herbicides in soils from southern Spain

BACKGROUND: Pesticide degradation and adsorption in soils are key processes determining whether pesticide use will have any impact on environmental quality. Pesticide degradation in soil generally results in a reduction in toxicity, but some pesticides have breakdown products that are more toxic than the parent compound. Adsorption to soil particles ensures that herbicide is retained in the place where its biological activity is expressed and also determines potential for transportation away from the site of action. Degradation and adsorption are complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behaviour of ionisable pesticides. This paper reports the sorption and degradation behaviour of four acidic pesticides in five soils from southern Spain. Results are used to investigate the influence of soil and pesticide properties on adsorption and degradation as well as the potential link between the two processes. RESULTS: Adsorption and degradation of four acidic pesticides were measured in four soils from Spain characterised by small organic matter (OM) contents (0.3-1.0%) and varying clay contents (3-66%). In general, sorption increased in the order dicamba < metsulfuron-methyl < 2,4-D < flupyrsulfuron-methyl-sodium. Both OM and clay content were found to be important in determining adsorption, but relative differences in clay content between soils were much larger than those in OM content, and therefore clay content was the main property determining the extent of herbicide adsorption for these soils. pH was negatively correlated with adsorption for all compounds apart from metsulfuron-methyl. A clear positive correlation was observed for degradation rate with clay and OM content (P < 0.01), and a negative correlation was observed with pH (P < 0.01). The exception was metsulfuron-methyl, for which degradation was found to be significantly correlated only with soil bioactivity (P < 0.05). CONCLUSIONS: Both OM and clay content were found to be important in determining adsorption, but relative differences in clay content between soils were much larger than those in OM content, and therefore clay content was the main property determining the extent of herbicide adsorption for soils of this type. pH was negatively correlated with adsorption for all compounds apart from metsulfuron-methyl. The contrasting behaviour shown for these four acidic pesticides indicates that chemical degradation in soil is more difficult to predict than adsorption. Most of the variables measured were interrelated, and different behaviours were observed even for compounds from the same chemical class and with similar structures.     

Adsorption,decomposition and movement of oxamyl in soil

A study was conducted of the behaviour of oxamyl in Israeli soils of varying clay and organic matter contents. The adsorption isotherms for oxamyl were linear, and the adsorption coefficient (K_d) could be correlated to the clay content of the soils, as well as to the organic matter content of the soil. Oxamyl adsorption was underestimated by using published correlations between the adsorption and the chemical properties of pesticides, such as their solubility or octan-1-ol-water partition coefficient. The decomposition of oxamyl in soils followed first-order kinetics. The half-life ranged from 4 to 33 days in a Bet Dagan soil. The reaction rate increased with increasing moisture content of the soil until field capacity was reached, at which point it levelled off. The Arrhenius relationship was followed, with degradation proceeding more rapidly at higher temperatures. In several soils of varying composition, which were kept at field capacity, no difference in the degradation rates was observed. Oxamyl was applied to a Bet Dagan soil from a point source in a single pulse, as a split application, and on a continuous basis. The distribution patterns of oxamyl under the various treatments differed significantly. After the single-pulse application, oxamyl was leached out of the emitter zone. While the split application decreased the oxamyl-free zone, the best results were obtained by continuous application, which gave a nearly uniform distribution of oxamyl in the soil.     

Adsorption, transport and degradation of fipronil termiticide in three Hawaii soils

BACKGROUND: The behavior of the termiticide fipronil in soils was studied to assess its potential to contaminate ground and surface water. This study characterizes (1) adsorption of fipronil in three different soils, (2) transport of fipronil through leaching and runoff under simulated rainfall in these soils and (3) degradation of fipronil to fipronil sulfide and fipronil sulfone in these soils. RESULTS: The adsorption experiments showed a Freundlich isotherm for fipronil with K_oc equal to 1184 L kg^?1. In the leaching experiments, the concentration of fipronil and its metabolites in leachate and runoff decreased asymptotically with time. The concentration of fipronil in the leachate from the three soils correlated inversely with soil organic carbon content. The degradation experiment showed that the half‐life of fipronil in the soils ranged from 28 to 34 days when soil moisture content was 75% of field capacities, and that 10.7–23.5% of the degraded fipronil was transformed into the two metabolites (fipronil sulfide and fipronil sulfone). CONCLUSION: Fipronil showed large losses through leaching but small losses via runoff owing to low volumes of runoff water generated and/or negligible particle‐facilitated transport of fipronil. The half‐life values of fipronil in all three soils were similar. Copyright © 2011 Society of Chemical Industry     

EVALUATION OF HERBICIDE PERSISTENCE IN SOIL*

Summary. The persistence of ten herbicides in soil was tested in the glasshouse over a 5–month period, using an oat bioassay. Simazine and diuron were highly persistent, atrazine persistent, fluometuron, trifluralin, bromacil and noruron moderately persistent, and pyrazon, prometryne and ametryne of short persistence. Six of these herbicides were also included in a field experiment consisting of logarithmically sprayed strips on which oats were sown at ten intervals of 1 month; changes of herbicidal activity with time were evaluated by measuring the length of the strip showing herbicidal injury. Results corroborate those of the glasshouse experiments except for trifluralin which was more persistent in the field. Disappearance curves were generally sigmoidal. The more persistent compounds showed a long period of slow disappearance followed by rapid disappearance.     

Adsorption and degradation of thiazopyr in compost‐amended and non‐amended soils

Adsorption and degradation of thiazopyr on two unamended soils and a soil amended annually during 8 years with compost were studied under laboratory conditions and compared with the results obtained on soils amended with fresh sewage sludge compost. The adsorption isotherms fitted the Freundlich equation well and a marked sorption increase was found in amended soils. Degradation data followed first‐order kinetics and thiazopyr had a half‐life of about 75 days at 25 °C and 60% water‐holding capacity of soil. The addition of fresh compost markedly decreased the rate of thiazopyr degradation, whereas the compost mineralised in the field after annual additions had only a small influence. Incubation studies with sterile soils showed a very significant decrease of the degradation rate, indicating that degradation by micro‐organisms was the main pathway of thiazopyr degradation in the soils studied. © 2001 Society of Chemical Industry     

七种农药在3种不同类型土壤中的吸附及淋溶特性

采用振荡平衡法和土柱淋溶法研究了2,4-滴酸、丁噻隆、毒草胺、炔草酸、氟环唑、甲基磺草酮和烯啶虫胺7种农药在江西红壤、太湖水稻土及东北黑土3种不同理化性质土壤中的吸附及淋溶特性,探讨了农药性质及土壤理化性质对供试农药在土壤中吸附、淋溶行为的影响。结果表明:农药的水溶性越大,其在土壤中的吸附性越弱,淋溶性越强;农药在土壤中的吸附性与土壤pH值、有机质含量以及阳离子交换量之间有较好的相关性。土壤pH值、有机质含量以及农药性质是影响农药在土壤中淋溶及迁移的主要因素。     

Limited survival of Ralstonia solanacearum Race 3 in bulk soils and composts from Egypt

Survival of Ralstonia solanacearum race 3 biovar 2 (phylotype II sequevar 1) in Egyptian soils and compost was studied under laboratory and field conditions. Survival of the pathogen under laboratory conditions varied with temperature, water potential and soil type, with temperature being the major determinant of survival of the pathogen. The effects of temperature and moisture content were variable between different experiments, but survival was generally longer at 15°C than at 4, 28 and 35°C respectively. Survival was also longer when moisture levels were constant compared with varying moisture levels at all temperatures. In experiments to compare the effects of progressive drying in sandy and clay soils there was a difference in survival times between the two soil types. In sandy soils, the pathogen died out more rapidly when soil was allowed to dry out than in controls where the soil was kept at constant water potential. In clay soils there was little difference between the two treatments, possibly due to the formation of a hard impermeable outer layer during the drying process, which retarded water loss from within. Survival in mature composts at 15°C was of the same order of magnitude as in soils but shorter at 28°C, possibly owing to increased biological activity at this temperature, or a resumption of the composting process, with concomitant higher temperatures within the compost itself. The maximum survival time recorded over all soil types and conditions during in vitro studies was around 200 days. In field studies, the maximum survival time in both bare sand and clay was around 85 days at depths up to 50 cm. The survival time was reduced in field experiments carried out in summer to less than 40 days and in one study when the ground was flooded for rice cultivation, the bacterium could not be detected 14 days after flooding. The maximum survival time of R. solanacearum in infected plant material or in infested soil samples incorporated into compost heaps was less than 2 weeks. At the culmination of field soil and compost experiments, no infection was detected in tomato seedlings up to 10 weeks after transplanting into the same soils or composts under glasshouse conditions at a temperature of 25°C.     

The biology of African feather grass (Pennisetum macrourum Trin.) in Tasmania, I. Seedling establishment

Seedling establishment of Pennisetum macrourum was studied in a series of glasshouse and field experiments. Maximum germination of 88% occurred at a constant temperature of 30C. In the glasshouse, highest seedling establishment was obtained from seeds buried 1 cm deep; it was less than 25% from seeds sown on the soil surface. Dormancy was induced in seeds buried 8 cm deep but only 6.4% remained viable after 6 months. Few viable seeds of P. macrourum were found in the soil and only one seedling was observed to establish in the field over a 20 month period. Up to 98% of seedlings transplanted into the field established successfully. The results suggest that reproduction by seed would not be a major problem in the control of P. macrourum.     

Screening for resistance to canker (Leptosphaeria maculans) in winter oilseed rape (Brassica napus ssp. oleifera)

A test involving infection of seedlings in a glasshouse was evaluated for potential use in screening breeding material by comparing the results with those of field tests. The two tests correlated well for some resistant selections, particularly those closely related to Jet Neuf, and for very susceptible selections. However, two small groups of selections were resistant in the field but consistently susceptible in the glasshouse. Inoculation of mature plants in the glasshouse resulted in similar discrepancies and therefore gave no advantage over the seedling test. These discrepancies limit the usefulness of glasshouse techniques for routine resistance screening. A very high correlation was found overall between internal and external canker symptoms of the crown in nine field trials. Significant differences were found, however, between selections and cultivars in the relative severity of these two symptoms. Upper stem canker and crown canker were found to be very poorly correlated for individual plants, but highly correlated for eultivar means. The significance of these observations is discussed with respect to scoring canker in the field.     

Does Fusarium‐caused seed mortality contribute to Bromus tectorum stand failure in the Great Basin?

Bromus tectorum (cheatgrass, downy brome) is an important invader in western North America, dominating millions of hectares of former semi‐arid shrubland. Stand failure or ‘die‐off’ is relatively common in monocultures of this annual grass. The study reported here investigated whether soil‐borne pathogens could be causal agents in die‐offs. Soils from two die‐off areas and adjacent B. tectorum stands were used in a glasshouse experiment with sterilised and non‐sterilised treatments. Soil sterilisation did not increase emergence, which averaged 80% in both die‐off and non‐die‐off soils. Seedling biomass was higher in die‐off soils, probably due to increased nitrogen availability. Fusarium was isolated from 80% of killed seeds in non‐sterilised soil treatments. In pathogenicity tests with 16 Fusarium isolates, host seeds incubated under water stress (?1.5MPa for 1 week prior to transfer to free water) suffered over twice the mortality of seeds incubated directly in free water (25–83% with water stress vs. 5–43% without water stress). These results suggest that soil‐borne Fusarium could play a role in B. tectorum stand failure in the field, but that low water stress conditions in the glasshouse experiment were not conducive to high levels of disease. Pathogenic Fusarium isolates were obtained from seeds planted in both die‐off and non‐die‐off soils, suggesting that microenvironmental factors that affect levels of water stress might be as important as relative abundance of soil‐borne pathogens in mediating spatial patterns of disease incidence in the field.     

EWRS Herbicide-Soil Working Group: Collaborative experiment on simazine persistence in soil

The effects of soil temperature and soil moisture content on the rate of simazine degradation were measured in the laboratory in soils from sixteen sites located in several different countries. First-order half-lives under standard incubation conditions were significantly correlated with clay content, organic carbon content and soil pH in a multiple linear regression. The temperature dependence of degradation was similar in the different soils whereas the moisture dependence showed considerable variation between soils. Persistence of simazine was also measured in the same soils in the field and at live additional sites. Weather records from the different sites for the periods of the Held experiments were used in conjunction with constants derived from the laboratory data in a computer program to simulate persistence in the field. In general, the model overestimated residues in the field. About half of the calculated residues were within 25% of those observed, an accuracy sufficient for practical purposes, but on several occasions the discrepancies between calculated and observed residues were greater than 50%. Possible reasons for the discrepancies and requirements for further experiments are discussed.     

氯胺嘧草醚在土壤中的吸附行为研究

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

Spread of levan-positive populations of <Emphasis Type="Italic">Pseudomonas savastanoi</Emphasis> pv. <Emphasis Type="Italic">savastanoi</Emphasis>, the causal agent of olive knot,in central Italy

Mixtures of wet vegetable wastes (Brassica, carrot or onion) and dry onion waste were composted at 50 °C for 7 days. The incorporation of the raw or composted vegetable waste mixtures into sandy loam, silt and peat soils reduced the viability of sclerotia of S. cepivorum in glasshouse pot bioassays. The reduction in viability was dependent on waste type, rate of incorporation, duration of exposure and soil type. Onion waste was the most effective waste type in reducing sclerotia viability in all three soils. The Brassica and carrot wastes were as effective as the onion waste in silt soil but less effective in sandy loam and peat soil. A 50% w/w incorporation rate of the wastes gave the largest reduction in viability, with an increase in reduction over time. Composted onion waste reduced sclerotia viability under glasshouse and field conditions although the effect was smaller in the field. Composted onion waste incorporated into soil at 50% w/w reduced the incidence of Allium white rot on onion seedlings in glasshouse pot tests. Incidence and control of the disease differed with soil type. The most consistent control was achieved in peat soil whereas no control was observed in silt soil. Incorporation of the waste 2 months prior to sowing or transplanting reduced seedling emergence in sandy loam soil and growth in all three soil types. The potential for field application of composted vegetable wastes as a sustainable method for control of Allium white rot and waste disposal is discussed.     

Adsorption and degradation of chlorsulfuron and metsulfuron-methyl in soils from different depths

Adsorption and degradation rates of chlorsulfuron and metsulfuron-methyl were measured in soil taken from depths of 0–20, 20–40 and 40–60 cm at eight sites. Adsorption of both herbicides was negatively correlated with soil pH, and positively correlated with soil organic matter content. When two soils with very high organic matter were excluded from the calculations, the correlations with organic matter content were no longer statistically significant but those with soil pH were affected only slightly. Degradation rates of both herbicides generally decreased with increasing depth in the soil and were positively correlated with microbial biomass and negatively correlated with soil pH. The possible significance of the results to persistence of the herbicides in the field is discussed.     

Simulation of the persistence of atrazine, linuron and metolachlor in soil at different sites in the USA

The effects of soil temperature and soil moisture content on the rates of degradation of atrazine, linuron and metolachlor were measured in the laboratory in soil from different sites in the USA. Persistence of the herbicides was measured in the same soils in the field during the summers of 1978 and 1979. Weather records from the different sites for the periods of the field experiments were used in conjunction with appropriate constants derived from the laboratory data in a computer program to simulate persistence in the field. There was a general tendency for the model to overestimate the observed soil residues. For example, with atrazine, 40 of the 48 measured residues were lower than those predicted by the model; seven were more than 30% below and two were more than 50% below. With metolachlor, 16 of the 48 measured residues were more than 30% below those predicted and six were more than 50% below; almost identical results were obtained with linuron. When the model overestimated late-season residues by a large amount, the discrepancies between predicted and observed data were usually apparent from early in the experiment. Possible reasons for the discrepancies are discussed.     

A new extraction method for benomyl residues in soil and its application in movement and persistence studies

A simple and rapid method for extracting benomyl residues from soils was compared with previous methods. Soil was extracted by shaking for 2 h at room temperature with (1:1) acetone/M aqueous ammonium chloride followed by clean-up by solvent partition and ultraviolet absorption estimation of carbendazim. Recoveries were comparable to those obtained by refluxing with methanolic hydrochloric acid for 4 h, hitherto the most efficient method reported, and were much greater than those obtained by extraction with ethyl acetate or chloroform. The new method gave more tractable extracts than those obtained by refluxing with methanolic hydrochloric acid, which form troublesome metal hydroxide precipitates during clean-up. In field experiments with 2-[¹⁴C]-benomyl and 2-[¹⁴C]-carbendazim, no radioactivity was found more than 25 mm from the soil surface during 10 months after surface application of 1 kg/ha. Carbendazim residues in soils from three field experiments indicated that its persistence is very sensitive to soil pH. The time for 50% loss of initial dose ranged from 26 months at pH 5.5 to less than 3 months at pH 7.2. Biological effectiveness in a crop may therefore depend markedly on differences in soil pH.     

The adsorption of atraton and monuron by soils at different water contents

Estimates of adsorption by soil at water contents down to less than wilting point were obtained with a three phase system of soil-water-immiscible organic solvent. The method is restricted to solutes with a water-organic solvent partition ratio of between about 10 and 0.5 if analytical errors are to be acceptable. With the two soils used the results with atraton and monuron were similar. There was little change in adsorption as soil water content was reduced until the level approached that needed to produce a monolayer on the soil surfaces, when it increased sharply. There were no differences at water contents between field capacity and wilting point.     

The degradation of simazine, linuron and propyzamide in different soils

Simazine, linuron and propyzamide were incubated in 18 different soils at 25°C and field capacity soil moisture content. The degradation of each herbicide followed first-order kinetics. The half-life of simazine varied from 20 to 44 days, that of linuron from 22 to 86 days and that of propyzamide from 10 to 32 days. The rate of linuron degradation was highly significantly correlated with soil organic matter content, clay content, soil respiration and the extent of herbicide adsorption by the soil. The rate of simazine degradation was significantly and negatively correlated with soil pH, but the rate of propyzamide degradation was not related with any of the soil factors examined.     

THE INFLUENCE OF ENVIRONMENT ON POTATO HAULM KILL BY DIQUAT AND ON ITS RESIDUES IN THE TUBERS

Summary. The effect of various environments on the degree of desiccation and of residues in King Edward and Majestic potatoes was studied. The higher residues frequently associated with the variety King Edward are ascribed from glasshouse experiments to greater diquat movement; they could not be accounted for by differences in uptake between the two varieties.
In glasshouse experiments, uptake was increased both by high air humidities and reduced light intensities before and after treatment. Since earlier work with cocksfoot and wheat indicated that dry soil conditions markedly increased movement, it is concluded that dull, humid air conditions associated with dry soil would be most conducive to efficient haulm desiccation and also to highest residues in the tubers. Late afternoon or evening treatment often provides thes conditions, and residues were in fact least from morning treatment.
In the field, increases in haulm desiccation were associated with reductions in residues. As they were observed only at light intensities below 5000 lux, they are unlikely to occur in normal dull weather.
Rain falling soon after spraying did not reduce the extent of haulm desiccation or diquat residues.
Influence de I'enviromurtunt sur la destruction des fanes de pomme de terre par le diquat el sur ses     

Adsorption of isoproturon,diuron and metsulfuron-methyl in two soils at high soil:solution ratios

Rates of degradation of isoproturon, diuron and metsulfuron-methyl were measured in two soils incubated at two temperatures (5 and 25 °C) with soil moisture at a matric potential of ?5 kPa. Rates of change in soil solution concentration were also measured after extraction of water from the soil using a centrifugation technique. The data, in general, indicated a more rapid rate of decline in aqueous-phase concentrations of herbicide than in total soil concentrations, and hence a progressive increase in partition coefficient in favour of the adsorbed phase^. In all of the incubations, however, adsorption of the herbicide was initially less than that measured using standard equilibration techniques that involved shaking with large volumes of solution relative to weights of soil. This may be explained by the ready availability of more adsorption sites in the shaken systems. With isoproturon and diuron, the changes in adsorption with time were similar at the two incubation temperatures. This indicates that the apparent changes in adsorption with these two compounds were not caused by preferential degradation in the soil solution, but by a slow equilibration with adsorption sites. The results with the weakly adsorbed compound metsulfuron-methyl, however, suggested the possibility of preferential degradation in the solution phase because, when degradation was slow, the absolute amounts adsorbed remained constant or increased slightly, even although solution concentrations declined. Implications of the results for pesticide behaviour in soils in the field are discussed.