Factors controlling degradation of pesticides in soil

Rates of pesticide degradation in soil exhibit a high degree of variability, the sources of which are usually unclear. Combining data from incubations performed using a range of soil properties and environmental conditions has resulted in greater understanding of factors controlling such degradation. The herbicides clomazone, flumetsulam, atrazine, and cloransulam-methyl, as well as the former insecticide naphthalene offer examples of degradation kinetics controlled by coupling competing processes which may in turn be regulated separately by environmental conditions and soil properties. The processes of degradation and volatilization appear to compete for clomazone in solution; sorbed clomazone is degraded only after the solution phase is depleted. Similarly, volatilization of naphthalene is enhanced when degradation has been inhibited by high nutrient levels. Degradation of the herbicide flumetsulam has been shown to be regulated by sorption, even though the compound has a relatively low affinity for the soil. The fate pathway for cloransulam-methyl shifts from mineralization to formation of metabolities, bound residues and physically occluded material as temperature increases. Atrazine degradation in soil may be controlled in part by the presence of inorganic nitrogen, as the herbicide appears to be used as a nitrogen source by micro-organisms. New insight gained from measurement of multiple fate processes is demonstrated by these examples.     

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.     

Tests of soil fertility following repeated applications of MCPA, tri-allate, simazine and linuron

The following herbicides were applied annually from 1963 to experimental plots of appropriate crops grown in monoculture: MCPA 1.7 kg ha^?1, triallate 1.7 kg ha^?1, simazine 1.7 kg ha^?1 and linuron 0.84 kg ha^?1 (applied twice per year). Before the eighth treatment in 1970, nutrient status, pH and growth in greenhouse tests of a range of plants were similar in soils from treated and control plots. There were no significant differences in yield when several test crops were grown in the field plots in 1977. In a similar experiment which ran for 6 years, the same herbicides were applied twice per year at twice the above rates on each occasion (three times a year at 1.7 kg ha^?1 in the case of linuron) to uncropped plots. Three years after the last treatment, there were no differences in extractable nutrients, pH, soil structure and crop yield on treated or control plots. These results support the conclusion from the main monitoring of the experiments reported elsewhere that annual treatments with these herbicides have had no adverse affect on the soil.     

Chlorpyrifos degradation in soil at termiticidal application rates

Chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate] is an organophosphorus insecticide applied to soil to control pests both in agricultural and in urban developments. Typical agricultural soil applications (0.56 to 5.6 kg ha^?1) result in initial soil surface residues of 0.3 to 32 μg g^?1. In contrast, termiticidal soil barrier treatments, a common urban use pattern, often result in initial soil residues of 1000 μg g^?1 or greater. The purpose of the present investigation was to understand better the degradation of chlorpyrifos in soil at termiticidal application rates and factors affecting its behaviour. Therefore, studies with [¹⁴C]chlorpyrifos were conducted under a variety of conditions in the laboratory. Initially, the degradation of chlorpyrifos at 1000 μg g^?1 initial concentration was examined in five different soils from termite-infested regions (Arizona, Florida, Hawaii, Texas) under standard conditions (25°C, field moisture capacity, darkness). Degradation half-lives in these soils ranged from 175 to 1576 days. The major metabolite formed in chlorpyrifos-treated soils was 3,5,6-trichloro-2-pyrid-inol, which represented up to 61% of applied radiocarbon after 13 months of incubation. Minor quantities of [¹⁴C]carbon dioxide (< 5%) and soil-bound residues (? 12%) were also present at that time. Subsequently, a factorial experiment examining chlorpyrifos degradation as affected by initial concentration (10, 100, 1000 μg g^?1), soil moisture (field moisture capacity, 1.5 MPa, air dry), and temperature 15, 25, 35°C) was conducted in the two soils which had displayed the most (Texas) and least (Florida) rapid rates of degradation. Chlorpyrifos degradation was significantly retarded at the 1000 μg g^?1 rate as compared to the 10 μg g^?1 rate. Temperature also had a dramatic effect on degradation rate, which approximately doubled with each 10°C increase in temperature. Results suggest that the extended (3–24 + years) termiticidal efficacy of chlorpyrifos observed in the field may be due both to the high initial concentrations employed (termite LC ₅₀ = 0.2– 2 μg g^?1) and the extended persistence which results from employment of these rates. The study also highlights the importance of investigating the behaviour of a pesticide under the diversity of agricultural and urban use scenarios in which it is employed.     

Persistence and degradation of chlorfenvinphos,chlormephos, disulfoton,phorate and pirimiphos-ethyl following spring and late-summer soil application

Granular formulations of chlorfenvinphos, chlormephos, disulfoton, phorate and pirimiphos-ethyl were broadcast at 2 kg a.i./ha and incorporated to 100 mm into a sandy-loam soil either in May or in September 1971. The relative persistence of their residues, including insecticidally active oxidation products, after both application dates was disulfoton > chlorfenvinphos > phorate > pirimiphos-ethyl > chlormephos. When applied in September all the insecticides persisted for longer than when applied in May. Degradation was slower during the winter while the mean soil temperature at 100 mm depth remained below 6 to 7°C. Rising soil temperature in the following spring rapidly increased the rates of degradation of chlorfenvinphos, chlormephos and pirimiphos-ethyl residues but not of disulfoton- and phorate-derived residues, predominantly the parent sulphones, which had been leached deeper. Ten months after the September application, half the total residues derived from disulfoton and phorate were found below the initial incorporation depth, whereas the other insecticides showed relatively little downward movement. It was concluded that late summer/early autumn applications for carrot fly control would leave appreciable residues of some insecticides in the soil at the beginning of the next growing season which may contribute to the terminal residues in crops. These would be minimised if moderately persistent compounds were used or if doses of persistent ones were substantially reduced.     

Photocatalytic degradation of pesticides and bio-molecules in water

Two approaches are suggested for the acceleration of the photocatalytic oxidation of organic contaminants of water: acceleration by oxidants and photo-enhancement by dyes. These processes were examined with several substances: two widely applied herbicides, bromacil (a uracil) and metribuzin (a triazine), and three proteins, studied as models of biocontaminated waters. The effects of oxygen and hydrogen peroxide indicated two different reaction patterns of photo-oxidation of the herbicides. With metribuzin, oxygen had a pronounced effect on the rate of photo-oxidation, while the influence of hydrogen peroxide was quite moderate; with bromacil, oxygen had a limited effect on the rate of photo-oxidation, which however was considerably enhanced by hydrogen peroxide. Acceleration of the photo-catalytic oxidation of colourless refractory contaminants by photo-excited dye was observed. Both UV and visible light were required for the enhanced decomposition. The mechanism of the reaction seems to involve a combination of oxidation by hydroxyl radicals, via the hole-electron semiconductor route, with subsequent oxidation of photo-intermediates by singlet oxygen formed by dye sensitization. The TiO2-photocatalyzed oxidation of proteins (albumin, ovalbumin and gamma-globulin) showed the susceptibility of proteins to photocleavage and of the amino acids to photocatalytic degradation. Tyrosine was the most sensitive, while the degradation of the aliphatic amino acids Gly and Asp was slow.     

Persistence of benomyl and thiophanate compounds in soil and various plants following soil application

Control ofSclerotinia sclerotiorum in muskmelons was obtained by a single soil drench with benomyl. The material was found in the apical parts of the plant and in the soil until the end of the growing season. Benomyl [methyl l-(butylcarbamoyl)-2-benzi-midazolecarbamate] and thiophanate methyl-NF 44 [1.2- bis (3 methoxycarbonyl-2-thioureido) benzene], applied to seedbeds, were taken up by and then persisted in tomato, pepper and eggplant for approximately 8 weeks after application. Thiophanate-NF 35 [1.2-bis (ethoxycarbonyl-2-thioureido) benzene] could be detected only in the bottom leaves of pepper and eggplant, for up to 4 weeks after application.     

基于量化反应性指数的氨基甲酸酯类农药定量构效关系研究

氨基甲酸酯类农药被广泛用于农业生产中,其作用机理主要是通过与乙酰胆碱酯酶共价结合,从而抑制其正常的生物活性,但此类农药的无节制使用导致其大量残留于生态环境中,对整个生态系统的生存安全造成了严重威胁.本文作者基于量化反应性指数,采用遗传/偏最小二乘法,对氨基甲酸酯与其对乙酰胆碱酯酶的抑制活性进行了定量构效关系研究.结果表...     

微生物降解农药的研究进展

在农药的微生物降解研究中,分离构建一种由天然微生物构成的复合系,将其应用于被污染的环境是消除农药污染的一个有效方法。本文综述了环境中降解农药的微生物种类、微生物降解农药的机理、在自然条件下影响微生物降解农药的因素及农药微生物降解研究方面的新技术和新方法。     

Kinetics of interaction of three carbamate pesticides with Indian soils: Aligarh district

The kinetics of interaction with soil of three carbamate pesticides (I, II, III) used as nematicides and herbicides was studied at four different temperatures from solutions of six soil samples of Aligarh district. The values obtained for rate constants for adsorption and desorption were in good agreement with those obtained from the Lindstrom model, which proved useful in the simultaneous evaluation of adsorption (k1) and desorption (k2) rate constants. The rate constants for pesticides were in the order III > I > II on all the six soil samples. The data for rate constants, activation energies, heats of activation, entropy of activation and thermodynamic parameters indicated a partly physical and partly chemical adsorption of pesticide on the soil surfaces. Adsorption occurred via coordination and/or protonation of the exchangeable cations with the amidic carbonyl group, and hydrogen bonding and dipole association at the crystal edge and basal surfaces. The adsorptivity of the soils may be attributed to the organic matter content and percentage clay content.     

The degradation of the herbicide benzoylprop-ethyl following its application to wheat

The herbicide benzoylprop-ethyl [SUFFIX,^a ethyl (±)-2-(N-benzoyl-N-3,4-di-chloroanilino) propionate] has been applied in a radiolabelled form to spring wheat and winter wheat growing both indoors and outdoors. During the application the compound also fell onto the soil. The plants and corresponding soils were examined at harvest at 71-98 days from treatment. Conversion of the herbicide occurred in plants and soil predominantly by a hydrolytic reaction to form benzoylprop^b followed in plants by its conjugation with sugars. Small amounts of N-benzoyl-3,4-dichloroaniline and benzoic acid were also detected in plants. There was no evidence for the presence of 3,4-dichloroaniline in the crops or soils nor was there evidence for 3,4,3′,4′-tetra-chloroazobenzene which has been implicated as a degradation product of some 3,4-dichloroaniline herbicides in soils. Residues on plants were greatest in the straw and consisted mainly of benzoylprop-ethyl and benzoylprop in free and conjugated forms. There was no evidence for appreciable movement of the compound within the plant from the treated foliage. Residues were particularly low in the grain and were not detected in the crop grown outdoors (limit of detectability 0.01 mg/kg). Residues in the soils were mainly in the 0-7.5 cm layer and there was no evidence for leaching below 15 cm.     

Routine methods for analysis of organophosphorus and carbamate insecticides in soil and ryegrass

The organophosphate insecticides dichlorvos, trichlorphon and isofenphos have been extracted from soil and ryegrass by blending with acetone+ benzene (19+1, v/v) and charcoal. After filtering, water and waxes were precipitated from the extract at ? 78°. The extracts were analysed for insecticide by gas chromatography using alkali flameionisation detection. Trichlorphon was converted to the acetate by on-column acetylation. Recoveries ranged from 73 to 93% for levels of insecticide from 0.1 to 10mg/kg. The carbamate insecticides methomyl and carbofuran plus the metabolite 2,3-dihydro-3-hydroxy-2,2-dimethylbenzofuran-7-yl methylcarbamate have been extracted from soil and ryegrass samples by shaking with acidified ammonium acetate. Following filtration and neutralisation, the aqueous phase was extracted with dichloromethane. The carbamates in the extracts were determined by gas chromatography using on-column trans-esterification to methyl methylcarbamate. Recoveries ranged from 79 to 97% for levels of insecticide from 0.1 to 10 mg/kg.     

A multiresidue analytical method for determining organochlorine,organophosphorus, dinitrophenyl and carbamate pesticides in apples

A multiresidue analytical method for the simultaneous extraction of organochlorine, organophosphorus, dinitrophenyl and carbamate pesticides from apples is presented. Extraction is performed with a mixture of toluene and hexane. After clean-up on a Florisil column, and in some cases conversion to derivatives, quantitative determination is performed by electron-capture gas chromatography. Qualitative verification is performed by thin-layer chromatography or gas chromatography-mass spectrometry.     

农药在植物中的内吸和传导行为与施药技术研究进展

农药的施用方式和施用效果与其在植物中的内吸和传导行为密切相关.农药在植物表面和内部的内吸和传导行为,不仅与其自身理化性质有关,还受植物种类、生长期、生长条件及施药方式等因素的影响.研究农药在植物体内的内吸和传导行为及其影响因素,对于选择合适的施药技术及提高农药利用率具有重要的指导意义.本文综述了农药在植物体内的内吸和传...     

The application of granular pesticides

Three basic processes are involved in the application of granular pesticides—metering, transporting and distributing. Metering may be simply dependent upon flow through an orifice under gravity but preferably force-feed mechanisms, usually driven in relation to forward speed are used. Transport may be effected merely under gravity, but pneumatics is also an accepted method particularly for large swath widths. Kinetic energy is also an agency in transporting granules as in “throwing” type distributors and this also achieves the distribution element. With gravity and pneumatic transport the final distribution is usually by spreaders or by nozzles at each outlet. Assessment of performance is rendered difficult by the very small size of the particles to be detected and the very low rates of application usually employed. Data are required on the appropriate sampling areas which should be used in assessing uniformity of distribution and the significance of the variations measured. Cooperation between all the disciplines of workers in the field is necessary for further development of the technique and in particular in the field of formulation a valuable contribution would be in the reduction in the diversity of physical properties of all the granular materials in use or projected.     

Enhanced degradation of some soil-applied herbicides

In a field experiment involving repeated herbicide application, persistence of simazine was not affected by up to three previous doses of the herbicide. With propyzamide, there was a trend to more rapid rates of degradation with increasing number of previous treatments. Persistence of linuron and alachlor was affected only slightly by prior applications. In a laboratory incubation with soil from the field that had received four doses of the appropriate herbicide over a 12–month period, there was again no effect from simazine pretreatments on rates of loss. However, propyzamide, linuron and alachlor all degraded more rapidly in the previously treated than in similar untreated soil samples. Propyzamide, linuron, alachlor and napropamide degradation rates were all enhanced by a single pretreatment of soil in laboratory incubations, whereas degradation rates of isoproturon, metazachlor, atrazine and simazine were the same in pretreated and control soil samples.     

园林生物农药及其使用技术浅谈

随着人们绿色环保意识的逐渐增强,利用生物农药控制病虫、杂草将成为今后园林绿地有害生物可持续控制的重要手段之一,应用会越来越广泛。本文结合园林管理实际,对生物农药从分类、特点及其使用技术等几个不同的角度作了较为系统的阐述,供广大园林绿化工作者参考。