Joint action of amino acid biosynthesis-inhibiting herbicides

The joint action of binary mixtures of the amino acid biosynthesis‐inhibiting herbicides glyphosate, glufosinate‐ammonium, metsulfuron‐methyl and imazapyr was assessed in pot experiments applying the Additive Dose Model (ADM). Plants of Sinapis arvensis or S. alba were sprayed with seven doses of the herbicides alone and binary fixed‐ratio mixtures of the four herbicides. In total, 73 binary mixtures were studied in six separate experiments. Mixtures of glyphosate and glufosinate‐ammonium were less phytotoxic than predicted by ADM whether commercial formulations or technical grade products were applied. In contrast, mixtures of glyphosate and metsulfuron‐methyl, glyphosate and imazapyr, glufosinate‐ammonium and metsulfuron‐methyl, glufosinate‐ammonium and imazapyr, and metsulfuron‐methyl and imazapyr either followed ADM or were synergistic. Synergism was observed most frequently for mixtures of glyphosate or glufosinate‐ammonium with metsulfuron‐methyl. Synergism was also more pronounced for commercial formulations of glyphosate and glufosinate‐ammonium than for the corresponding technical grade formulations, implying that synergism was caused by the presence of the formulation constituents of the commercial glyphosate and glufosinate‐ammonium formulations in the spray solution.     

Modelling herbicide dose and weed density effects on crop:weed competition

The effects of a range of herbicide doses on crop:weed competition were investigated by measuring crop yield and weed seed production. Weed competitivity of wheat was greater in cv. Spark than in cv. Avalon, and decreased with increasing herbicide dose, being well described by the standard dose–response curve. A combined model was then developed by incorporating the standard dose–response curve into the rectangular hyperbola competition model to describe the effects of plant density of a model weed, Brassica napus L., and a herbicide, metsulfuron‐methyl, on crop yield and weed seed production. The model developed in this study was used to describe crop yield and weed seed production, and to estimate the herbicide dose required to restrict crop yield loss caused by weeds and weed seed production to an acceptable level. At the acceptable yield loss of 5% and the weed density of 200 B. napus plants m^–2, the model recommends 0.9 g a.i. metsulfuron‐methyl ha^–1 in Avalon and 2.0 g a.i. in Spark.     

Analysis of metsulfuron‐methyl residues in wheat field soil: a comparison of HPLC and bioassay techniques

BACKGROUND: Metsulfuron‐methyl is a low‐application‐rate sulfonylurea herbicide that is widely used to control broad‐leaved weeds in wheat. Owing to its persistent nature, its residues may be present at phytotoxic levels for the next crop in rotation. Therefore, a comparative evaluation of HPLC and bioassay techniques was made for the analysis of this herbicide in wheat field soil. RESULTS: Metsulfuron‐methyl was applied to wheat crop at different rates (4, 8 and 12 AI ha^?1) at 28 days after sowing as a post‐emergence application, and the soil was analysed for metsulfuron‐methyl residues by HPLC and lentil seed bioassay techniques. The bioassay was found to be the more sensitive technique. At the recommended rate of application, 4 g AI ha^?1, the bioassay technique could detect the residue up to 30 days in surface soil, while, with HPLC, residues were not detectable on the 15th day. The half‐lives of metsulfuron‐methyl by HPLC and bioassay were calculated as 6.3–7.8 and 17.5 days respectively. Under field conditions, residues of metsulfuron‐methyl were also detected in subsurface soil by the bioassay technique at trace levels, but were not detected by the solvent extraction/HPLC method. CONCLUSION: Lentil seed bioassay is a more sensitive technique than HPLC. Traces of residues detected in subsurface soil indicated the mobility of metsulfuron‐methyl into lower layers. Copyright © 2009 Society of Chemical Industry     

Modelling interactions between herbicide dose and multiple weed species interference in crop–weed competition

The effects of a range of herbicide doses on crop–multiple weed competition were investigated. Competitivity of Galium aparine was approximately six times greater than that of Matricaria perforata with no herbicide treatment. Competitivities of both weeds decreased with increasing herbicide dose, being well described by the standard dose–response curve with the competitivity of M. perforata being more sensitive than that of G. aparine to a herbicide mixture, metsulfuron‐methyl and fluroxypyr. A combined model was then developed by incorporating the standard dose–response curve into the multivariate rectangular hyperbola competition model to describe the effects of multiple infestation of G. aparine and M. perforata and the herbicide mixture on crop yield. The model developed in this study was used to predict crop yield and to estimate the herbicide dose required to restrict crop yield loss caused by weeds to an acceptable level. At the acceptable yield loss of 5% and the weed combination of 120 M. perforata plants m^?2 and 20 G. aparine plants m^?2, the model recommends a mixture of 1.2 g a.i. ha^?1 of metsulfuron‐methyl and 120 g a.i. ha^?1 of fluroxypyr.     

Modelling the effects of sub-lethal doses of herbicide and nitrogen fertilizer on crop–weed competition

The effects of sub‐lethal dose of herbicide and nitrogen fertilizer on crop–weed competition were investigated. Biomass increases of winter wheat and a model weed, Brassica napus, at no‐herbicide treatment with increasing nitrogen were successfully described by the inverse quadratic model and the linear model respectively. Increases in weed competitivity (β₀) of the rectangular hyperbola and parameter B in the dose–response curve for weed biomass, with increasing nitrogen were also successfully described by the exponential model. New models were developed by incorporating inverse quadratic and exponential models into the combined rectangular hyperbola with the standard dose–response curve for winter wheat biomass yield and the combined standard dose—response model with the rectangular hyperbola for weed biomass, to describe the complex effects of herbicide and nitrogen on crop–weed competition. The models developed were used to predict crop yield and weed biomass and to estimate the herbicide doses required to restrict crop yield loss caused by weeds and weed biomass production to an acceptable level at a range of nitrogen levels. The model for crop yield was further modified to estimate the herbicide dose and nitrogen level to achieve a target crop biomass yield. For the target crop biomass yield of 1200 g m^?2 with an infestation of 100 B. napus plants m^?2, the model recommended various options for nitrogen and herbicide combinations: 140 and 2.9, 180 and 0.9 and 360 kg ha^?1 and 1.7 g a.i. ha^?1 of nitrogen and metsulfuron‐methyl respectively.     

苯磺隆·甲磺隆·氯磺隆混合物的液相色谱分析

本文以甲醇 水 冰乙酸为流动相，采用C18不锈钢柱，检测波长240nm，对苯磺隆、甲磺隆、氯磺隆混合物进行反相高效液相色谱定量分析。该方法的标准差别分别为0.081、0.013和0.013，变异系数为0.886%、0.268%和0.256%，回收率为99.39%、99.29%和99.28%，线性相关系数为苯磺隆r=0.9994、甲磺隆r=0.9992、氯磺隆r=0.9991，线性方程为苯磺隆y=1360088.17x 1389384、甲磺隆y=972186.69X-21262.8、氯磺隆y=789773.50X 86258.8。     

水稻不同品种或组合对甲磺隆耐药性差异的机制研究

以水稻乙酰乳酸合成酶(ALS)比活力为研究对象,通过在离体和活体条件下比较其对甲磺隆的敏感性水平,探讨了水稻不同品种或组合的耐药性差异机制。结果表明,离体条件下不同水稻品种或组合ALS对甲磺隆均较敏感,当甲磺隆浓度为100 μg/L时,对ALS比活力抑制率达60%以上,且活力百分比与甲磺隆浓度对数成直线负相关关系,相关程度显著或极显著;活体条件下ALS活力均受到甲磺隆不同程度的抑制,但同一品种ALS活力不随甲磺隆浓度的变化而呈现规律性变化。在甲磺隆浓度相同时,活体条件下所有供试水稻品种ALS活力均显著高于离体条件下的ALS活力,影响程度与植株耐药性差异基本一致,说明甲磺隆在水稻体内存在较强代谢失活作用,代谢失活差异是水稻不同品种或组合对甲磺隆的耐药性差异机制。     

Testing the performance of registered herbicides on the control of Campuloclinium macrocephalum (Asteraceae) in South African grasslands

We report on the performance of the registered herbicides picloram and metsulfuron‐methyl on the control of Campuloclinium macrocephalum (pompom weed) in grasslands. Herbicide trials in hydric and xeric grasslands were treated for three consecutive years in either summer (February) or autumn (April) and monitored for an additional 3 years after spraying ceased. Uncontrolled factors such as a host‐specific rust, fire and drought were observed from the second year of the study. Metsulfuron‐methyl and picloram did not differ in efficacy according to the timing of applications, but average mortality of marked plants was <80% expected of registered herbicides. Populations of C. macrocephalum in plots were reduced proportionately to the percentage mortality of marked plants. Picloram and metsulfuron‐methyl applied at 252 g a.i. ha^?1 and 45 g a.i. ha^?1, respectively, were not detectable by gas chromatography in the upper 25 cm of the soil profile during any of the sampling intervals from 0 to 56 days after treatment. Three annual applications of registered herbicide did not reduce C. macrocephalum successfully, and it is estimated that between five (summer) to seven (autumn) annual treatments are required to reduce weed density to <1 plant per plot (25 m²). Future research should focus on rust–herbicide interactions, the role of fire in seedbank management and fire as a treatment that could be integrated with chemical control.     

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.     

Mechanism of resistance to bensulfuron-methyl in Alisma plantago-aquatica biotypes from Portuguese rice paddy fields

Two Alisma plantago‐aquatica biotypes resistant to bensulfuron‐methyl were detected in rice paddy fields in Portugal’s Mondego (biotype T) and Tagus and Sorraia (biotype Q) River valleys. The fields had been treated with bensulfuron‐methyl‐based herbicide mixtures for 4–6 years. In order to characterize the resistant (R) biotypes, dose–response experiments, absorption and translocation assays, metabolism studies and acetolactate synthase (ALS) activity assays were performed. There were marked differences between R and susceptible (S) biotypes, with a resistance index (ED₅₀R/S) of 500 and 6.25 for biotypes Q and T respectively. Cross‐resistance to azimsulfuron, cinosulfuron and ethoxysulfuron, but not to metsulfuron‐methyl, imazethapyr, bentazone, propanil and MCPA was demonstrated. No differences in the absorption and translocation of ¹⁴C‐bensulfuron‐methyl were found between the biotypes studied. Maximum absorption attained 1.12, 2.02 and 2.56 nmol g⁻¹ dry weight after 96 h incubation with herbicide, for S, Q and T biotypes respectively. Most of the radioactivity taken up by the roots was translocated to shoots. Bensulfuron‐methyl metabolism in shoots was similar in all biotypes. The R biotypes displayed a higher level of ALS activity than the S biotype, both in the presence and absence of herbicide and the resistance indices (IC₅₀R/S) were 20 197 and 10 for biotypes Q and T respectively. These data confirm for the first time that resistance to bensulfuron‐methyl in A. plantago‐aquatica is target‐site‐based. In practice, to control target site R biotypes, it would be preferable to use mixtures of ALS inhibitors with herbicides with other modes of action.     

Hydrolysis of triasulfuron,metsulfuron‐methyl and chlorsulfuron in alkaline soil and aqueous solutions

The hydrolysis of triasulfuron, metsulfuron‐methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH‐sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2–6.2) than under neutral and moderately alkaline conditions (8.2–9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo‐first‐order kinetics. There were no significant differences (P = 0.05) in the rate constants (k, day⁻¹) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the ‘rate constant’ on pH. The hydrolysis involving attack by neutral water was at least 100‐fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O‐demethylation of metsulfuron‐methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural alkaline soils. © 2000 Society of Chemical Industry     

Examination of bound (non-extractable) residues of MCPA and flamprop in wheat straw

The long term metabolism of [¹⁴C]MCPA and [¹⁴C]flamprop in wheat (Triticum aestivum) straw was found to involve incorporation of radioactivity as residues that were insoluble in acetone+water (1+1 by volume). A chemical and an enzymic solubilisation procedure were critically evaluated in attempts to release these residues for further examination. The chemical procedure resulted in complete solubilisation of all the radioactivity of both compounds in association with more than one cell wall fraction. However, routine quantitative analysis was found to be difficult for some fractions. Furthermore, the extracts did not appear to be suitable for investigation of the nature of the binding with the plant constituents. None of the enzymes employed in the enzymic procedures released significant amounts of the residues insoluble in the aqueous acetone. Despite these problems, the residues of MCPA that were insoluble in aqueous acetone were found to contain both the parent MCPA and its major metabolite 4-chloro-α-hydroxy-o-tolyloxyacetic acid.     

A monoclonal antibody‐based ELISA for the analysis of the insecticide flucythrinate in environmental and crop samples

A competitive enzyme‐linked immunosorbent assay (ELISA) has been developed for the detection of the insecticide flucythrinate in environmental and food samples. Two types of haptens, the acid moiety that is the hydrolyzed product of flucythrinate, and the carboxylated propyl derivative of the alcohol moiety, were used to prepare monoclonal antibodies (MAbs). Five MAbs, which raised against the former hapten, were reactive with flucythrinate. Among them, MAb F1A27‐4 showed the highest activity toward flucythrinate, and did not cross‐react with other pyrethroids such as cycloprothrin, fenvalerate, fluvalinate, etofenprox and silafluofen. The assay conditions of indirect competitive ELISA with MAb F1A27‐4 were studied to optimize the detection of flucythrinate in environmental and food samples. Incubation at 4 °C in the assay buffer, pH 8, with 300 mM sodium chloride improved the sensitivity. The addition of rabbit serum albumin or rabbit antiserum and the presence of 50 ml litre^?1 of methanol reduced matrix effects of the samples. Under optimized conditions, the ELISA detected flucythrinate spiked in water, soil, and extracts of apple and tea samples down to 10 mg litre^?1, 0.2 mg litre^?1, 0.3 mg litre^?1 and 0.3 mg litre^?1, respectively. The mean recovery and CV ranged from 91% to 120% and from 5% to 12%, respectively. The ELISA results in apple samples correlated well with those from LC–MS analysis (r² = 0.99, n = 12). © 2001 Society of Chemical Industry     

The control of Achillea millefolium in the Snowy Mountains of Australia

The response of Achillea millefolium L. to herbicides was measured to determine the effectiveness of the current recommendations and to test alternative herbicides. Five plots at each of the three replicate sites were selected and randomly treated with one of the four herbicides: dicamba/2,4‐D, glyphosate, metsulfuron‐methyl and triclopyr/picloram. After 12 months, the recommended treatment, dicamba/2,4‐D, did not cause a significant reduction in aerial biomass compared with untreated controls and the number of flowering stems was significantly increased in treated plots. Metsulfuron‐methyl and triclopyr/picloram caused a significant reduction in A. millefolium aerial biomass but did not affect the number of flowering stems. Glyphosate produced a significant reduction in aerial biomass and was less effective. These results suggest that the current recommendation for A. millefolium might be improved. Site‐specific effects such as aspect may also influence the effectiveness of herbicides on this species.     

Response of Brassica napus in tissue culture to metsulfuron-methyl and chlorsulfuron

A herbicide bioassay based on tissue cultures of Brassica napus L. was evaluated with selected sulfonylurea herbicides. Data were analysed by fitting the results to a log-logistic dose–response model. Within an experiment, the non-linear regression models were fitted simultaneously to the individual dose–response curves. The results obtained showed good response to even low concentrations of herbicide, with detection limits in the range 0.008–0.69 nmol L^?1 for chlorsulfuron and 0.02–0.13 nmol L^?1 for metsulfuron. The reproducibility of the assays, on the basis of coefficient of variation of the ED₅₀ values, was found to be 44% for chlorsulfuron and 48% for metsulfuron measurements. Assay of herbicide dissolved in aqueous soil extract showed significant interference from this matrix on the response, requiring a five times dilution of the extract to overcome this matrix effect.     

农产品中基质对酶联免疫分析法检测三唑磷残留的干扰及消除研究

基质干扰是免疫法检测食品中农药残留时经常碰到的问题。以胡萝卜、菠菜、香蕉、梨、稻米和花生等为试材,研究了不同农产品基质对酶联免疫分析法(ELISA)检测三唑磷的影响。结果表明:不同农产品基质对ELISA检测的干扰机制不同,香蕉主要是抑制了辣根过氧化物酶的活性,菠菜、梨和稻米则主要是干扰了抗原和抗体的结合反应,胡萝卜和花生不仅抑制酶的活性,同时还干扰了抗原和抗体的结合反应。将这些农产品的磷酸盐缓冲液(PBS)(含2.5%甲醇)提取液用含有质量分数为0.3%的脱脂奶粉、0.1%的乙二胺四乙酸(EDTA)和含2.5%甲醇的PBS稀释10倍,在12000r/min下离心10min,即可消除其对ELISA检测的干扰。研究结果表明, ELISA法是可用于农产品中三唑磷残留检测的一种简单、快速、有效的方法。     

Sensitivity of Botrytis cinerea to chitosan and acibenzolar‐S‐methyl

BACKGROUND: The antifungal properties of chitosan and acibenzolar‐S‐methyl were evaluated to assess their potential for protecting grapes against Botrytis cinerea Pers.: Fr. isolated from Vitis vinifera L. The objectives were to determine the effects of these compounds on the in vitro development of B. cinerea and to assess their effectiveness at controlling grey mould on grapes stored at different temperatures. RESULTS: Both agents significantly inhibited the radial growth of this fungus species. The EC₅₀ was 1.77 mg mL^?1 for chitosan and 3.44 mg mL^?1 for acibenzolar‐S‐methyl. In addition, single grapes treated with aqueous solutions of chitosan (1.0 and 2.5 mg mL^?1) and acibenzolar‐S‐methyl (1.0 and 3.0 mg mL^?1) were inoculated with B. cinerea and incubated at both 4 and 24 °C. After 4 days at 24 °C, all the concentrations of chitosan and acibenzolar‐S‐methyl significantly reduced B. cinerea growth. However, at 4 °C, significant differences were only observed between chitosan at 2.5 mg mL^?1 and acibenzolar‐S‐methyl at both 1.0 and 3.0 mg mL^?1 and the corresponding controls. After 3 days at 24 °C, the greatest reduction in lesion size was obtained in grapes pretreated with acibenzolar‐S‐methyl at 3.0 mg mL^?1. Only the highest doses of these products significantly reduced the lesion diameters when grapes were stored for 3 days at 4 °C. CONCLUSIONS: Chitosan and acibenzolar‐S‐methyl could directly inhibit the growth of Botrytis cinerea in vitro and confer resistance on grapes against grey mould. Pretreatment with these compounds could be an alternative to traditional fungicides in post‐harvest disease control in grapes. Copyright © 2010 Society of Chemical Industry     

Biological responses of a non‐target aquatic plant (Nasturtium officinale) to the herbicide,tribenuron‐methyl

To assess its response to the herbicide, tribenuron‐methyl, samples of Nasturtium officinale were exposed to 0, 0.01, 0.05, 0.1, and 0.5 mg L^?1 of tribenuron‐methyl for 1, 2, 4 and 7 days. The influence of this herbicide on the relative growth rate, electrolyte leakage, lipid peroxidation, photosynthetic pigmentation, protein content, and performance of anti‐oxidant enzymes, such as superoxide dismutase (SOD), catalase, and ascorbate peroxidase (APX), was examined. The results indicated that tribenuron‐methyl, applied at 0.5 mg L^?1, affected plant growth negatively. It also was determined that chlorophyll a is the most responsive photosynthetic pigment to tribenuron–methyl exposure. Under stress conditions, the anti‐oxidant enzymes were up‐regulated compared to the control. The SOD activity was significantly stimulated, while the activity of APX was inhibited. A significant correlation was found between lipid peroxidation and SOD activity. The exposure period and herbicide concentration had significant effects on the biological responses against tribenuron‐methyl stress. These results may be useful for clarifying the effect of herbicides on non‐target aquatic plants.     

Evaluation of the combination of 1,3-dichloropropene and dazomet as an efficient alternative to methyl bromide for cucumber production in China

BACKGROUND: The combination of 1,3‐dichloropropene (1,3‐D) and dazomet (DZ) offers a potential alternative to methyl bromide (MB) for soil disinfection. MB is scheduled to be withdrawn from routine use by 2015 in developing countries. Combination treatments of 1,3‐D + DZ were evaluated in a laboratory study and in two commercial cucumber fields. RESULTS: Laboratory studies found that nearly all of the tested combinations of 1,3‐D and DZ displayed positive synergistic activity on root‐knot nematodes (Meloidogyne spp.), two major soilborne fungi (Fusarium spp. and Phytophthora spp.) and the seeds of two major weed species (Digitaria sanguinalis and Abutilon theophrasti). Field trials revealed that the combination of 1,3‐D and DZ (at 10 + 25 g m^?2) successfully suppressed Meloidogyne spp. root galling, sharply reduced Fusarium spp. and Phytophthora spp. and maintained high cucumber yields. The combination treatment of 1,3‐D + DZ was more effective than 1,3‐D or DZ alone and provided results similar to methyl bromide with respect to pest control, plant mortality, plant height, yield and income. All of the treatments were significantly better than the non‐treated control. CONCLUSION: The results indicate that the tested combination of 1,3‐D and DZ offers an efficient alternative to methyl bromide for cucumber production. Copyright © 2012 Society of Chemical Industry     

Application of Solid Phase Micro‐Extraction (SPME) to the analysis of pesticide residues in vegetables

Solid Phase Micro‐Extraction (SPME) is a new analytical technique, based on capturing the analytes by adsorption onto an organic phase coating a glass fibre, and subsequent direct desorption into the injector of a gas chromatograph. This technique has been successfully applied in the analysis of organic contaminants in water, giving linear responses and, in some cases, high sensitivities. The present paper reports data about the application of SPME to the analysis of pesticide residues in a vegetable matrix, testing over nearly one hundred active compounds, with two types of adsorbent phase (polydimethylsiloxane and Carbowax/divinylbenzene). A vegetable matrix spiked with pesticides was analyzed by SPME and by a traditional multi‐residue method; recoveries were determined and compared for the two cases. The behaviour of the analytical response by SPME was studied in the range 0.01–1 mg kg⁻¹ by adding increasing amounts of given pesticide mixtures to the vegetable matrix. The procedure was further tested by analyzing real samples, and gave some difficulties in recovering the whole amount of some of the residues present (in comparison with the traditional method). The SPME method was then improved by pre‐extracting with acetone and sonicating before the extraction/adsorption step. The results obtained were satisfactory (some certified matrices were also tested) with good accordance between the two methods. Nevertheless some active compounds showed very low responses or remained undetectable by SPME in our experimental conditions. © 2000 Society of Chemical Industry