农用微生物杀菌剂剂型研究进展

农用微生物杀菌剂的主要剂型有粉剂(DP)、可湿性粉剂(WP)、颗粒剂(GR)、水分散粒剂(WG)和悬浮剂(SC)等。我国现有的农用微生物杀菌剂剂型种类较为单一,主要为可湿性粉剂,未来应加强其他剂型如水分散粒剂和悬浮剂等的研究开发。生防菌的活菌数、制剂加工和贮存条件以及田间环境因素等对农用微生物杀菌剂的防效均有很大影响,科学合理地评价这些影响,并研究其形成原因和内在规律,对农用微生物杀菌剂的深入研究开发具有重要意义。文章从剂型种类、性质、质量控制以及生产条件、贮存条件和田间环境条件对制剂性质与防效的影响等方面,对农用微生物杀菌剂剂型的研究现状和存在问题进行了详细的综述,并分析了其未来发展趋势。     

Intercalation of the herbicide atrazine in layered double hydroxides for controlled-release applications

BACKGROUND: The herbicide atrazine was intercalated in the interlayer region of Mg/Al layered double hydroxides in order to produce a nanohybrid that could be used in controlled‐release applications. RESULTS: The hydrophobic herbicide was incorporated in artificial membranes formed in the interlayer of the inorganic host by using palmitic acid. The synthetic nanohybrid material was characterised by various techniques, and release studies were carried out. In addition, the photosynthetic alga Chlamydomonas reinhardtii Dang. was treated with the atrazine‐containing nanohybrid, which exerted an herbicidal efficacy similar to that of the free herbicide. CONCLUSION: The herbicide containing nanohybrid could enable a controlled release of the herbicide. In addition, the herbicide would be delivered close to its site of uptake, enhancing efficiency and reducing the required doses. Copyright © 2011 Society of Chemical Industry     

Field leaching of pesticides at five test sites in Hawaii: modeling flow and transport

BACKGROUND: Physically based tier‐II models may serve as possible alternatives to expensive field and laboratory leaching experiments required for pesticide approval and registration. The objective of this study was to predict pesticide fate and transport at five different sites in Hawaii using data from an earlier field leaching experiment and a one‐dimensional tier‐II model. As the predicted concentration profiles of pesticides did not provide close agreement with data, inverse modeling was used to obtain adequate reactive transport parameters. The estimated transport parameters of pesticides were also utilized in a tier‐I model, which is currently used by the state authorities to evaluate the relative leaching potential. RESULTS: Water flow in soil profiles was simulated by the tier‐II model with acceptable accuracy at all experimental sites. The observed concentration profiles and center of mass depths predicted by the tier‐II simulations based on optimized transport parameters provided better agreements than did the non‐optimized parameters. With optimized parameters, the tier‐I model also delivered results consistent with observed pesticide center of mass depths. CONCLUSION: Tier‐II numerical modeling helped to identify relevant transport processes in field leaching of pesticides. The process‐based modeling of water flow and pesticide transport, coupled with the inverse procedure, can contribute significantly to the evaluation of chemical leaching in Hawaii soils. Copyright © 2011 Society of Chemical Industry     

Sorption-desorption of flucarbazone and propoxycarbazone and their benzenesulfonamide and triazolinone metabolites in two soils

Sorption-desorption interactions of pesticides with soil determine the availability of pesticides in soil for transport, plant uptake and microbial degradation. These interactions are affected by the physical and chemical properties of the pesticide and soil and, for some pesticides, their residence time in the soil. While sorption-desorption of many herbicides has been characterised, very little work in this area has been done on herbicide metabolites. The objective of this study was to characterise sorption-desorption of two sulfonylaminocarbonyltriazolinone herbicides, flucarbazone and propoxycarbazone, and their benzenesulfonamide and triazolinone metabolites in two soils with different physical and chemical properties. K(f) values for all four chemicals were greater in clay loam soil, which had higher organic carbon and clay contents than loamy sand. K(f-oc) ranged from 29 to 119 for the herbicides and from 42 to 84 for the metabolites. Desorption was hysteretic in every case. Lower desorption in the more sorptive system might indicate that hysteresis can be attributed to irreversible binding of the molecules to soil surfaces. These data show the importance of characterisation of both sorption and desorption of herbicide residues in soil, particularly in the case of prediction of herbicide residue transport. In this case, potential transport of sulfonylaminocarbonyltriazolinone herbicide metabolites would be overpredicted if parent chemical soil sorption values were used to predict transport.     

Reduced metribuzin pollution with phosphatidylcholine-clay formulations

BACKGROUND: Metribuzin is a widely used herbicide that has been identified as a groundwater contaminant. In this study, slow‐release formulations of metribuzin were designed by encapsulating the active ingredient in phosphatidylcholine (PC) vesicles and adsorbing the vesicles onto montmorillonite. RESULTS: The maximum active ingredient content in the slow‐release formulations was 246 g kg^?1. Infrared spectroscopy results revealed that the hydrophobic interactions between metribuzin and the alkyl chains on PC were necessary for encapsulation. In addition, water bridges connecting the herbicide and the PC headgroup enhanced the solubility of metribuzin in PC. Adsorption experiments in soils were performed to evaluate the relationship between sorption and leaching. Funnel experiments in a sandy soil revealed that the herbicide was not irreversibly retained in the formulation matrix. In soil column experiments, PC–clay formulations enhanced herbicide accumulation and biological activity in the top soil layer relative to a commercial formulation. PC–clay formulations also reduced the dissipation of metribuzin by a factor of 1.6–2.5. CONCLUSIONS: A reduction in the recommended dose of metribuzin can be achieved by employing PC–clay formulations, which reduces the environmental risk associated with herbicide applications. Moreover, PC and montmorillonite are non‐toxic and do not negatively affect the environment. Copyright © 2010 Society of Chemical Industry     

Preparation of controlled-release formulations of 14C-labelled thiobencarb herbicide and study of their environmental behaviour

Controlled-release formulations of ¹⁴C-labelled thiobencarb herbicide were prepared in calcium alginate using kaolin as an inexpensive filler. The rates of release of the herbicide from these and from a commercial granular formulation were studied in static distilled water contained in open and closed vessels. The rate of release of the herbicide was much higher from the commercial formulation than from the controlled-release formulations. Increasing the proportion of kaolin to calcium alginate in controlled-release formulations reduced the rate of release of the herbicide. There was a significant loss of thiobencarb-related radioactivity from the water solution when the vessels containing the solutions were left uncovered and exposed to light. The loss of the herbicide seemed to be due to degradation and evaporation.     

Development of herbicides for paddy rice in Japan

The history of the development of herbicides for mechanized paddy rice production in Japan can be characterized by a combination of products with several ingredients, by large availability in formulation, and by application methods for labor saving in accordance with natural and social conditions of the country, for instance, around 40% of national land located in hilly and mountainous areas, small size paddy fields consolidated in approximately 0.3 ha on average and so on. As for combination products, one‐shot herbicides that can control both annual and perennial weeds, including grasses, sedges and broadleaved weeds, mainly with sulfonylureas have been a major means of rice production since the 1980s. One‐shot herbicides have been improved by using newly developed chemicals with excellent herbicidal efficacy, such as acetolactate synthase (ALS), 4‐hydroxyphenylpyruvate dioxygenase (4‐HPPD), protoporphyrinogen oxidase (PPO) and very‐long‐chain fatty acid elongase (VLCFAE) inhibitors, and by combining ingredients that are effective against sulfonylurea‐resistant (SU‐R) biotypes of lowland weeds. The latest type of one‐shot herbicides can control noxious species such as Eleocharis kuroguwai as well as other ordinal species. Regarding herbicide formulation, “1 kg granule,” “Jumbo,” “Flowable,” “Diffusion granule” and so on have been developed to save farmers the troubles of applying herbicides. As for application methods, “at‐transplanting application,” “at‐irrigation inlet application” and utilization of radio‐controlled helicopters or boats were put into practical use as labor‐saving technology. As a result, farmers were spared the severe hand‐weeding work under blazing heat during the summer season. Japan Association for Advancement of Phyto‐Regulators (JAPR) have promoted and contributed to the development of herbicides through collaboration with agrochemical companies and research organizations since it was founded in 1964. In this paper, I explain the development progress of herbicide using materials on the mode of action, the trend of one‐shot herbicides, the feature of a labor‐saving formulation and the working hours for weed management in rice production.     

The impact of uptake, translocation and metabolism on the differential selectivity between blackgrass and wheat for the herbicide pyroxsulam

BACKGROUND: Wheat shows selectivity to pyroxsulam, a new broad‐spectrum herbicide with high activity on blackgrass. Studies were performed to establish whether uptake, translocation or metabolism were responsible for the differential activity in wheat compared with blackgrass. In addition, the effect of the safener cloquintocet‐mexyl on metabolism was evaluated in wheat and blackgrass shoots. RESULTS: Root uptake of pyroxsulam in blackgrass was significantly higher than in wheat, suggesting a possible activity enhancement in blackgrass owing to root uptake. Translocation to foliage from root uptake as well as translocation out of treated foliage following foliar applications was low in wheat compared with blackgrass, likely owing to the rapid metabolism of pyroxsulam in wheat. Wheat metabolized pyroxsulam significantly faster than blackgrass to the less active O‐dealkylation product. Wheat shoots metabolized pyroxsulam faster when the safener cloquintocet‐mexyl was present, but cloquintocet‐mexyl did not increase the rate of metabolism in blackgrass. CONCLUSIONS: The selectivity of pyroxsulam to wheat relative to blackgrass was connected primarily with differences in the rate of metabolism and generation of an inactive metabolite. Metabolism in wheat restricted subsequent movement of radioactivity out of the treated leaf. The rapid metabolism in wheat was increased by the addition of cloquintocet‐mexyl. Copyright © 2010 Society of Chemical Industry     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

环糊精及其衍生物在农药领域应用的研究进展

环糊精及其衍生物具有 "内疏水、外亲水"的特殊分子结构,可与许多客体分子包结形成包合物。环糊精与农药形成包合物对农药分子具有增溶、控制释放、提高稳定性等功能,在农药制剂方面具有重要的应用价值。环糊精对农药污染物的降解有促进作用,对农药分子具有选择性识别作用,因而在农药污染物治理、农药残留检测方面也有重要的应用价值。综述了环糊精及其衍生物在作为农药剂型加工中的助剂、农药污染物治理和农药残留检测等方面应用的研究新进展,并对其在农药领域的发展趋势和应用前景进行了展望。     

农药剂型和制剂与农药的剂量转移

本文简要介绍了关于农药剂量转移问题的研究动向 ,农药剂型和制剂对于剂量转移过程的影响以及通过农药剂型和制剂研究设计对剂量转移过程进行调控的一些成功实例。这些研究工作表明 ,剂型和制剂同农药使用技术的紧密结合对于农药的作用方式和毒理会发生影响 ,也可以有助于减轻或消除农药对人体和环境的危害。农药剂型和制剂的研究不仅涉及加工方法和加工技术问题 ,实际上已经发展成为一门新的边缘科学 ,即“农药剂型毒理学”。以剂型毒理学的研究为基础进行农药剂型和使用技术的研究开发 ,将会为农药科学开辟出崭新的领域并获得新的机遇和成功。     

Are pre‐spraying growing conditions a major determinant of herbicide efficacy?

To evaluate the effect of pre‐spraying growing conditions on herbicide efficacy, two years of experimentation were conducted in which Persicaria maculosa plants were exposed to different light intensities for 1–4 days before metribuzin treatment. Specific leaf area, rather than plant growth rate or plant size, was the only parameter that correlated well with herbicide efficacy in both years of experimentation. The negative relationship between the ED₅₀ and the specific leaf area indicates that leaf characteristics might be an important determinant of herbicide efficacy, for instance through an effect on herbicide uptake. In the third year of experimentation this hypothesis was further investigated by raising six cohorts of weed plants at a 1‐week interval and thus exposing them to a range of weather conditions. Clear relationships between uptake and herbicide efficacy were found for a combination of four plant species (Solanum nigrum, Senecio vulgaris, Chenopodium album and Brassica napus) and two herbicides (phenmedipham and bentazone). For phenmedipham, uptake was negatively correlated with global radiation and positively correlated with relative humidity. For the herbicide bentazone the opposite was found. These results were not species‐specific. This study shows the importance of the sensitivity of herbicide × species combinations and indicates that pre‐spraying weather information is relevant for the development of reduced dose rate recommendations.     

Considering degradation kinetics of pesticides in plant uptake models: proof of concept for potato

BACKGROUND

Degradation kinetics of pesticides in plants are crucial for modeling mechanism-based pesticide residual concentrations. However, due to complex open-field conditions that involve multiple pesticide plant uptake and elimination processes, it is difficult to directly measure degradation kinetics of pesticides in plants. To address this limitation, we proposed a modeling approach for estimating degradation rate constants of pesticides in plants, using potato as a model crop. An operational tool was developed to backward-estimate degradation rate constants, and three pesticides were selected to perform example simulations.

RESULTS

The simulation results of thiamethoxam indicated that the growth dynamics of the potato had a significant impact on the degradation kinetic estimates when the pesticide was applied during the early growth stage, as the size of the potato determined the uptake and elimination kinetics via diffusion. Using mepiquat, we demonstrated that geographical variations in weather conditions and soil properties led to significant differences in the dissipation kinetics in both potato plants and soil, which propagated the variability of the degradation rate constant. Simulation results of chlorpyrifos differed between two reported field studies, which is due to the effect of the vertical distribution of the residue concentration in the soil, which is not considered in the majority of recent studies.

CONCLUSIONS

Our proposed approach is adaptable to plant growth dynamics, preharvest intervals, and multiple pesticide application events. In future research, it is expected that the proposed method will enable region-specific inputs to improve the estimation of the degradation kinetics of pesticides in plants. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Resistance Mechanism of Propanil-Resistant Barnyardgrass: II. In-vivo Metabolism of the Propanil Molecule

Propanil-resistant barnyardgrass populations, previously verified in Arkansas rice fields and in greenhouse tests, were examined in the laboratory to ascertain if the resistance mechanism in this weed biotype was herbicide metabolism. Propanil-resistant barnyardgrass was controlled >95% in the greenhouse when carbaryl (an aryl acylamidase inhibitor) was applied two days prior to propanil. Laboratory studies with ¹⁴C-radiolabelled propanil indicated that the herbicide was hydrolysed in propanil-resistant barnyardgrass and rice to form 3,4-dichloroaniline, but no detectable hydrolysis occurred in susceptible barnyardgrass. Two additional polar metabolites were detected in propanil-resistant barnyardgrass and rice and tentatively identified by thin layer chromatography. Overall, metabolites in the resistant barnyardgrass had R_f values similar to those in rice, indicating similar metabolism for both species. These data, coupled with data from a previous report on the resistant biotype showing no differential absorption/translocation or molecular modification of the herbicide binding site in the resistant biotype, indicate that the resistance mechanism is metabolic degradation of propanil. © of SCI.     

Status of black grass (Alopecurus myosuroides) resistance to acetyl-coenzyme A carboxylase inhibitors in France

We assessed the contributions of target site‐ and non‐target site‐based resistance to herbicides inhibiting acetyl‐coenzyme A carboxylase (ACC) in Alopecurus myosuroides (black grass). A total of 243 A. myosuroides populations collected across France were analysed using herbicide sensitivity bioassay (24 300 seedlings analysed) and ACC genotyping (13 188 seedlings analysed). Seedlings resistant to at least one ACC‐inhibiting herbicide were detected in 99.2% of the populations. Mutant, resistant ACC allele(s) were detected in 56.8% of the populations. Among the five resistant ACC alleles known in A. myosuroides, alleles containing an isoleucine‐to‐leucine substitution at codon 1781 were predominant (59.5% of the plants containing resistant ACC alleles). Comparison of the results from herbicide sensitivity bioassays with genotyping indicated that more than 75% of the plants resistant to ACC‐inhibiting herbicides in France would be resistant via increased herbicide metabolism. Analysis of herbicide application records suggested that in 15.9% of the populations studied, metabolism‐based resistance to ACC‐inhibiting herbicides was mostly selected for by herbicides with other modes of action. Our study revealed the importance of non‐target site‐based resistance in A. myosuroides. Using herbicides with alternative modes of action to control populations resistant to ACC‐inhibiting herbicides, the recommended management approach, may thus be jeopardised by the widespread occurrence of metabolism‐based resistance mechanisms conferring broad‐spectrum cross‐resistance.     

Metabolism of the phosphonate herbicide glyphosate by a non-nitrate-utilizing strain of Penicillium chrysogenum

A Penicillium chrysogenum strain was isolated for its ability to grow in minimal medium containing the herbicide glyphosate as the only nitrogen source. The presence of concentrations up to 25 mM progressively stimulated the fungal growth rate, which was negligible in media lacking reduced nitrogen. However, glyphosate utilization never exceeded 1 mmol g-1 mycelial dry mass, and below a threshold concentration both herbicide uptake and fungal growth were subject to a lag phase, suggesting that the herbicide may enter the cell by either simple passive diffusion or inducible carriers. Amino acids, possible products of glyphosate breakdown, as well as ammonia, were found to replace the herbicide in restoring mycelial growth. Cells were devoid of detectable nitrate reductase activity, thus the isolate seems to be impaired in its ability to convert nitrate to ammonium. In vitro activity of 5-enol-pyruvyl-shikimate-3-phosphate synthase, the target site of glyphosate action, was highly sensitive to the herbicide. Fungal growth rate was considerably lower when the herbicide was also the only phosphorus source, whereas glyphosate utilization was substantially unaffected, suggesting an unusual route for its degradation. Herbicide metabolism was strongly reduced when other sources of organic nitrogen were made available.     

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.     

Uptake, translocation and metabolism of aminocyclopyrachlor in prickly lettuce, rush skeletonweed and yellow starthistle

BACKGROUND: Aminocyclopyrachlor is a new herbicide proposed to control broadleaf weeds and shrubs in non‐crop and rangeland systems. To gain a better understanding of observed field efficacy, the uptake and translocation of foliar‐applied aminocyclopyrachlor (DPX‐MAT28) and aminocyclopyrachlor methyl ester (DPX‐KJM44) were evaluated in two annuals, prickly lettuce (Lactuca serriola L.) and yellow starthistle (Centaurea solstitialis L.), and one perennial, rush skeletonweed (Chondrilla juncea L.). RESULTS: Absorption and translocation varied between species. While absorption of DPX‐KJM44 was greater than absorption of DPX‐MAT28, rush skeletonweed absorbed the most, followed by yellow starthistle and prickly lettuce. Overall, the total translocation of either herbicide was highest in yellow starthistle, followed by rush skeletonweed and prickly lettuce. Proportional herbicide movement between species was similar, with the majority translocating to developing shoots. However, in rush skeletonweed, early translocation was directed to root tissue. In rush skeletonweed, no DPX‐MAT28 metabolism occurred, while DPX‐KJM44 was rapidly de‐esterified and translocated as DPX‐MAT28. CONCLUSION: Aminocyclopyrachlor absorption and translocation are dependent on active ingredient structure and species sensitivity. Highly sensitive species such as prickly lettuce absorb and translocate less material than relatively less sensitive species such as rush skeletonweed. De‐esterification of DPX‐KJM44 appears to delay translocation of the resulting acid in yellow starthistle and rush skeletonweed. Copyright © 2011 Society of Chemical Industry