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

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

Adsorption–desorption of 2,4-D by hydroxy aluminium montmorillonite complexes

Adsorption–desorption characteristics of 2,4-dichlorophenoxyacetic acid (2,4-D) on pure montmorillonite and synthetic chlorite-like complexes [Al(OH)_x-montmorillonite complexes, obtained by coating montmorillonite surfaces with different amounts of Al(OH)_x] were investigated. The equilibrium adsorption of 2,4-D was described by both Langmuir and Freundlich type isotherms. The extent of adsorption as well as the type of interaction between adsorbate and adsorbent was affected by the nature of incubation buffer and the charge characteristics of supports. At pH 5·6 and in acetate buffer, 2,4-D was negatively adsorbed by montmorillonite and herbicide adsorption capacity increased with increasing amounts of Al(OH)_x species loaded on montmorillonite surfaces. When adsorption experiments were performed at the same pH but in phosphate buffer, strong reductions of both the amount of adsorbed pesticide and its affinity for the adsorbents were measured. Evidently, phosphate anions competed strongly with 2,4-D anions for the sorption site on chlorite-like complexes. Furthermore, desorption tests revealed that a large amount (about 60%) of the pesticide was firmly bound to the clay and was not removed even after repeated washings or 24 h exposure to desorption solution. Both electrostatic interactions between the negative COO^- moieties of 2,4-D and the positive sites on clays, and ligand exchanges of COO^- groups with -OH or water at the clay surface were probably involved in the adsorption process. ©1997 SCI     

Uptake, translocation and fate of 2,4-D and chlorsulfuron in Silene vulgaris (Moench) Garcke

Experiments were conducted to examine the up take, translocation and metabolism by S. vulgaris of two distinctly different herbicides: 2,4-D, a phenoxyalkanoic acid with growth regulator activity to which this species exhibits complete tolerance, and chlorsulfuron, a sul-fonylurea to which S. vulgaris is highly sensitive. Despite their structural dissimilarities 2,4-D and chlorsulfuron was readily absorbed by S. vulgaris with 65 and 69%, respectively, of the applied dosage being absorbed within 72 hours after treatment. Approximately 35% of the 2,4-D and 10% of the chlorsulfuron label was translocated out of the treated leaf after 72 hours. Neither herbicide accumulated in the terminal bud. Seventy-two hours after treatment 63% of the recovered ¹⁴C remained as unaltered 2,4-D in S. vulgaris, while in tomato, a 2,4-D sensitive species, 65% of the recovered ¹⁴C remained as intact herbicide. In S. vulgaris approximately 86% of the radioactivity remained as intact chlorsulfuron 72 hours after treatment compared to 12% in the tolerant wheat. The tolerance of S. vulgaris to 2,4-D could not be accounted for by limited absorption, translocation nor metabolic degradation of the herbicide. The sensitivity of S. vulgaris to chlorsulfuron would appear to be related to the inability of this species to metabolize the herbicide molecule.     

Soil persistence experiments with [14C]2,4-D in herbicidal mixtures, and field persistence studies with tri-allate and trifluralin both singly and combined

The persistence of [¹⁴C]2,4-D at a rate equivalent to 1 kg/ha was studied in the laboratory on a heavy clay and a sandy loam at 85%of field capacity and 20°C both alone and in the presence of 1 kg/ha dicamba, dichlorprop, difenzoquat, TCA, and 2,4,5-T. The persistence of 2,4,5-T was also monitored in both soils under the same conditions in the presence and absence of [¹⁴C]2,4-D. All soils were extracted at weekly intervals using aqueous acidic acetonitrile and analysed for [¹⁴C]2,4-D remainining radiochemical techniques. The extracts containing 2,4.5-T were additionally analysed gas chromatographically for that herbicide. In each soil type the half-life of the 2,4-D was similar regardless of whether applied singly or in combination with the five herbicides tested. Similarly, [¹⁴C]2,4-D did not affect the breakdown of 2,4,5-T in either soil type. The persistence of tri-allate (1·5 kg/ha) and trifluralin (0·75 kg/ha) both singly and in combination were compared using small field plots at two locations in Saskatchewan. Applications were made during May of 1977 and 1978 and the plots were sampled and analysed for herbicide(s) remaining after 10 and 20 weeks, respectively. The results indicate that within experimental error the loss of both tri-allate and trifluralin from the plots treated with the mixture was the same as from plots treated with the individual compounds.     

STUDIEN ZUR VERTEILUNG VON 14C-MARKIERTEM 2,4-D IN VERSCHIEDEN EMPFINDLICHEN UNKRÄUTERN

Studies of the absorption and translocation of ¹⁴C-2,4-D in Chenopodium album L., Galinsoga parviflora Cav., Datura stramonium L. and Galium aparine L. in relation to their susceptibility gave the following results: In G aparine (resistant) there was little transport of 2,4-D applied to the leaves, and a probable relationship between resistance and the immediate binding of the 2,4-D in the treated leaf. D. stramonium (relatively resistant) transported 2,4-D in considerable amounts alter uptake through the leaf, while C. album (very susceptible) and G. parviflora (susceptible) were intermediate in respect of 2,4-D translocation. No relationship between susceptibility of these four species and 2,4-D uptake and translocation from the leaves could be established. After application to the root systems of the four species, 2,4-D was taken up and translocated in the shoot to varying extents. In G. aparine much 2,4-D was taken up and translocated. In contrast to leaf application, the herbicide was not immediately converted into a strongly-held immobile form. In C. album, G. parviflora and D. stramonium, however, no 2,4-D was translocated in the shoot. There was thus no correlation between susceptibility and shoot transport of 2,4-D in the four species studied. Distribution du 2,4-D marqué au ¹⁴C dans des espèces de mauvaises herbes présentant des sensibilités diverses     

UNTERSUCHUNGEN ÜBER AUFNAHME UND TRANSLOKATION VON 14C-MARKIERTEN HERBIZIDEN IN AGROSTEMMA GITHAGO L. UND TUSSILAGO FARFARA L.

Studies of the uptake and translocation of ¹⁴C-labelled 2, 4-D, MCPA and aminotriazole in Agrostemma githago L. and Tussilago farfara L. clarified the behaviour of the herbicides in both species. In A. githago, MCPA was more freely mobile than 2,4-D after application to the leaf; it was distributed in the plant more rapidly and in greater quantity. Similarly, following root uptake MCPA was transported in the shoot in greater amounts than was 2,4-D. There is a clear relationship between the susceptibility of A. githago to MCPA and the mobility of the herbicide in the plant. In T. farfara, 2,4-D and aminotriazole applied to the leaves were equally well absorbed and relatively rapidly translocated. During the period up to 72 h the amounts of herbicide in the plant increased to similar levels; after that, ¹⁴C activity in plants treated with 2,4-D fell slightly whereas there was further accumulation of aminotriazole. Following uptake through the roots, translocation and accumulation in the leaves were considerably greater with aminotriazole than with 2,4-D. The lack of accumulation of 2,4-D could be a factor in the resistance of T. farfara to this herbicidie. Recherches sur l'absorption et la migration d'herbicides marqués au ¹⁴ C dans Agrostemma githago L. et Tussilago farfara L.     

Spatial and temporal distributions of 1,3-dichloropropene in soil under drip and shank application and implications for pest control efficacy using concentration–time index

A field experiment was conducted to study the spatial and temporal distributions of (EZ)-1,3-dichloropropene (1,3-D) in the soil and effects on pest control efficacy. An emulsifiable concentrate formulation of 1,3-D (Telone EC) was applied with drip irrigation at 47 kg AI ha⁻¹ to two different depths (2.5 and 20.3 cm, respectively). Comparisons were made between the two drip treatments and a direct shank injection of 1,3-D (Telone II) at 112 kg AI ha⁻¹. Concentrations of 1,3-D in soil air were measured at several locations over time to determine the spatial and temporal characteristics, and to calculate the concentration–time index (CT). Citrus nematodes (Tylenchulus semipenetrans) were placed in the fumigated soil at 25 cm depth and their mortality rates were compared to the calculated CT. Distributions of 1,3-D were found to be relatively uniform in both the drip irrigation and the shank injection treatment. An application rate of 47 kg ha⁻¹ with drip irrigation was sufficient to achieve significant concentration levels in soil beds. Applying 1,3-D with direct shank injection at 112 kg ha⁻¹ extended the measurable concentration levels to the furrows between the soil beds and to a depth of 1 m below the soil surface. Effective control of T. semipenetrans was achieved with both the drip irrigation and the shank injection. A threshold soil 1,3-D CT value of 12 μg h cm⁻³ was needed to reach a 100% efficacy for T. semipenetrans. The study indicates that 1,3-D fumigation may be carried out with drip irrigation at very low rate, and a CT index may be derived to aid in the determination of a minimum effective dosage. © 1999 Society of Chemical Industry     

基于AquaCrop模型的夏玉米生长模拟及灌溉制度优化

为评价AquaCrop模型在关中地区的适用性并寻求最佳的灌溉制度,对夏玉米在不同灌溉与施氮水平下的生长进行模拟和验证,并利用校验后的模型研究了3种不同降雨年型以及11种灌溉模式下夏玉米产量和水分利用效率的变化特征。结果表明：AquaCrop模型可以较好地模拟关中地区不同灌溉与施氮水平下夏玉米产量和生物量,模型模拟的产量与实测值之间的决定系数（R²）、均方根误差（RMSE）、标准均方根误差（NRMSE）、符合度指数（d）和纳什效率系数（E_NS）分别为0.919、0.249 t·hm^-2、4.112、0.977和0.915;对于地上部生物量,模拟值与实测值的R²、RMSE、NRMSE、d和E_NS分别为0.860、0.977 t·hm^-2、6.407、0.933和0.694。利用校验后的模型分析了试验区内3种不同降水年型条件下11种灌溉模式的夏玉米产量和水分利用效率的变化特征,依据模拟结果及夏玉米生理需水规律,同时为了实现高产和高水分利用效率,得出不同年型的优化灌溉制度为：若能保证出苗整齐,湿润年可不灌水,此时也能获得较高产量和水分利用效率;平水年推荐在拔节期灌水60 mm,能节约50%水资源,亦能保证稳产;干旱年推荐在拔节期和抽雄期各灌水60 mm,可获得高产和高水分利用效率。     

Pre-baiting for increased acceptance of zinc phosphide baits by voles: an assessment technique

During a product-performance test of 2% zinc phosphide (Zn₃P₂) steam-rolled-oat groats (11.2 kg ha⁻¹) to control voles (Microtus spp) in alfalfa (Medicago sativa), randomly located, brushed-dirt plots were used to assess broadcast distribution and removal/acceptance of placebo particles. Results showed that the Spyker® Model-75 Spreaders were calibrated adequately, with placebo baits broadcast uniformly onto plots [x ± SD = 3.5 (±2.7) groats 930 cm⁻¹]. Acceptance of the placebos by voles increased rapidly – 28% and 60% by 24 h and 48 h post-broadcast, respectively. Analyses of variance confirmed the uniformity (non-significance) of particles broadcast among enclosures/plots and the significantly greater removal/acceptance of placebos across days. This technique affords an objective decision-making tool for applicators and researchers applying Zn₃P₂ baits in field situations – an objective technique of assessing pre-bait acceptance that should improve efficacy of the rodenticide. © 1999 Society of Chemical Industry     

Differential effects of phenoxy herbicides on light-dependent CO2 fixation in isolated cells of C3 and C4 plants

Cells were isolated from the developing leaves of Ipomoea aquatica and Digitaria sanguinalis. The effects of phenoxy alkanoic acid herbicides on light-dependent ¹⁴CO₂ fixation and oxygen evolution in these leaf cells were studied. (2,4-Dichlorophenoxy)acetic acid and (2,4,5-trichlorophenoxy) acetic acid (2,4,5-T and 2,4-D) caused a 20% stimulation of ¹⁴CO₂ fixation at 0.8 × 10⁻⁵M and an inhibition at 1 × 10⁻⁴M in I. aquatica leaf cells. Temperature seemed to have a marked influence on such action. No effect or very little effect was observed in the leaf cells of D. sanguinalis. The nonactive (2,4,6-Trichlorophenoxy)acetic acid (2,4,6-T) caused a similar stimulation of CO₂ fixation as 2,4-D and 2,4,5-T at low concentrations in I. aquatica leaf cells, but no inhibition was observed at high concentration. Increase of hight intensity increased the rate of CO₂ fixation in both control and 2,4,6-T-treated cells; however, the percentage of stimulation remained the same. At stimulatory concentration, all three compounds did not cause any stimulation in either photosystem I and II or photosystem II-mediated oxygen evolution. At higher concentrations, the differential effects of 2,4-D and 2,4,5-T on the light-induced CO₂ fixation and photosystem II-mediated oxygen evolution in the I. aquatica leaf cells and D. sanguinalis mesophyll (ms) cells may be attributed in part to their selective action against dicotyledonous plants.     

Control of Solatium karsensis in grain sorghum

Solatium karsensis Symon, an Australian native perennial, has become an important weed in irrigated summer crops in far western New South Wales. A screening trial of 14 herbicides showed that atrazine was the most effective treatment, though 2,4-D also suppressed S. karsensis in grain sorghum (Sorghum bicolor L. cv. Rico) for the duration of the crop. Grain sorghum yields were higher in plots treated with atrazine at 2–5 kg (a.i.) ha^?1 than for any other herbicide treatment or the untreated control. Because the root system remained viable annual herbicide application would be necessary for the continued control of 5. karsensis.     

Cuticular penetration of 2,4-D as affected by interaction between a diethylene glycol monooleate surfactant and apple leaf cuticles

Impacts of pH and sorption-desorption of ‘Pegosperse’ 100-O (PEG. 100-O; diethylene glycol monooleate, containing 15% diester) surfactant by apple (Malus pumila M.) leaf cuticles on surfactant-enhanced cuticular penetration of 2,4-D [(2,4-dichlorophenoxy)acetic acid] were studied. Glass cylinders were affixed to enzymatically isolated adaxial apple leaf cuticles after the cuticle segments had been soaked in 10 ml liter^?1 PEG 100-O solution and washed for 20 and 120 min, respectively. Quantities of [¹⁴C]2,4-D in the glass-cuticle chambers passing through the cuticles at pH values from 1 to 6 5 were determined. PEG 100-O significantly increased cuticular penetration of dissociated 2,4-D at pH 4–5; the surfactant had no effect on penetration of undissociated 2,4-D at pH 10. Surfactant-enhanced penetration of 2,4-D occurred only when the surfactant was in the cuticles, while the process of surfactant sorption-desorption alone had no effect on penetration. These results support a ‘hydrophilic channel’ hypothesis, i.e. that surfactants may create hydrophilic channels or increase the area of the channels in the cuticle and, consequently, enhance the passing of polar molecules like dissociated 2,4-D through the cuticle.     

Effects of temperature and concentration of the accelerators ethoxylated alcohols,diethyl suberate and tributyl phosphate on the mobility of [14C]2,4‐dichlorophenoxy butyric acid in plant cuticles

Intrinsic activities of monodisperse ethoxylated dodecanols (MEDs), diethyl suberate (DESU) and tributyl phosphate (TBP) were investigated using Stephanotis floribunda leaf cuticular membranes (CMs) and [¹⁴C]2,4‐dichlorophenoxy butyric acid (2,4‐DB) as a model solute. When sorbed in cuticular membranes, MEDs, DESU and TBP increase solute mobility and are called accelerators for this reason. With MEDs, dose‐effect curves (log mobility vs accelerator concentration) were linear but, with DESU and TBP, curves convex to the x axes were obtained that approached a maximum at 90 and 150 g kg⁻¹, respectively. Accelerators increased the mobility of 2,4‐DB in the CMs by 9‐ to 48‐fold, and effects were larger at lower temperatures (range 15–30 °C). Activation energy for diffusion of 2,4‐DB was 105 kJ mol⁻¹, decreasing with increasing accelerator concentrations to 26 kJ mol⁻¹ with DESU at 90 g kg⁻¹ and 64 kJ mol⁻¹ with TBP at 150 g kg⁻¹. Thus, the intrinsic activity of DESU was much higher than that of TBP, which implies that, for a given effect, less DESU than TBP would be needed. MEDs were also very effective accelerators, lowering activation energies to 36 kJ mol⁻¹. Data are discussed in relation to increasing rates of foliar penetration of active ingredients at low temperatures. © 2001 Society of Chemical Industry     

DIE WIRKUNG DER HERBIZIDE 2,4-D, AMITROL, ATRAZIN, CHLORPROPHAM UND CHLORFLURENOL AUF DIE NUCLEINSÄURE-BIOSYNTHESE DES ASCOMYCETEN NEUROSPORA CRASSA

Zusammenfassung. Es wurde die DNS- und RNS-Biosynthese von Neurospora crassa Wildstamm 3a6A unter Einfluss unterschiedlicher Konzentrationen von 2,4-D, Amitrol, Atrazin, Chlorpropham und Chlorflurenol untersucht. Die Variation der Herbizide erfolgte von 10^?3 bis 10^?6 M. Der in beliifteten Kulturen gezüchtete Pilz ist gegenuber Chlorpropham am empfindlichsten. Bei 10^?3 M ist die Toxizitätsgrenze überschritten und das Wachstum vollständig gehemmt. 2,4-D hat in einer Konzentration von 10^?3 M den grössten Einfluss auf die Nucleinsäure-Biosynthese. Die DNS-Werte erhöhen sich gegenüber der Kontrolle aiif 140%. Unter Einfluss von Atrazin (10^?3 M) scheint besonders die Protein-Synthese stimuliert zu werden. Die Zunahme beträgt hier fast 140%. Allgemein haben die untersuchten 5 Herbizide einen relativ geringen Einfluss auf die Nucleinsäure-Biosynthese. Ein grösserer Effect ist nur bei der höchsten Herbizid-Konzentration von 10^?3 M ZU erkennen. Der Pilz ist gegenüber diesen Herbiziden wenig empfindlich. Effets des herbicides 2,4-D, aminotriazole, atrazine, chlorprophame et chlorflurénol sur la biosynthése de l'acide nucléique chez un ascomycéte; Neurospora crassa Résumé. La biosynthése de l'ADN et de l'ARN fut déterminée chez la race sauvage 3a6A de Neurospara crassa, cultivé sur des milieux contenant du 2, 4-D, de l'aminotriazole, de l'atrazine, du chlorprophame et du chlorflurenol à des concentrations de 10^?3 a 10^?6 M. En culture aéréc, JV. crassa fut plus sensible au chlorprophame et à 10^?3 M. sa croissance fut complétement inhibée. L'effet le ptus marqué sur la biosynthésc de I'acide nucléique fut observé avec lc 2,4-D à 10^?3 M. concentration qui porta la teneur en ADN à 140% de celle du téemoin. Avec l'atrazine à 10^?3 M. la synthése des proteines en particulier sembla stimulée jusqu’à atteindre environ 140% du témoin. En général, les cinq herbicides etudids n'eurent qu'un effet relativement faibie sur la biosynthése de l'acide nucléique; seule la concentration la plus forte, 10^?3 M. cut un effet appreciable. N. crassa ne se montra pas tres sensible à ces herbicides. Effects of the herbicides 2,4-D, aminotriazole, atrazine, chlorpropham and chlorflurenol on nucleic-acid biosynthesis in the ascomycete Neurospora crassa Summary. Biosynthesis of DNA and RNA was determined in Neurospora crassa wild race 3a6A grown in cultures containing 2,4-D, aminotriazole, atrazine, chlorpropham and chlorflurenol in concentrations of 10^?3-10^?6 M. In aerated culture, N. crassa was most sensitive to chlorpropham and at 10^?3 M growth was completely inhibited. The greatest effect on nucleic-acid biosynthesis was given by 2,4-D at 10^?3 M which increased the DNA value to 140% of the control. With atrazine at 10^?3 M. protein synthesis in particular appeared to be stimulated, to almost 140% of the control. In general, the five herbicides studied had a relatively slight effect on nucleic-acid biosynthesis; only with the highest concentration of 10^?3 M was the effect appreciable. N. crassa was not very susceptible to these herbicides.     

2,4-Dichlorophenoxyacetic acid (2,4-D) and paranitrophenol (PNP) interactions with gills of Anodonta californiensis and Mytilus californianus: Uptake and effects on membrane fluxes

The effects of pesticides and their breakdown products on membrane fluxes is a subject of interest in assessing the potential ecological impact of these substances. As part of a continuing program we have examined the effects of 2,4-dichlorophenoxyacetic acid (2,4-D) and paranitrophenol (PNP) on divalent cation and primary amine losses from and glycine uptake by gills of the bivalve molluscs Anodonta californiensis (fresh water) and Mytilus californianus (marine). Both 2,4-D and PNP reduce glycine influx into gills of M. californianus. This observation is consistent with the view that glycine is bound to the gill surface as a Mg²⁺ complex prior to active transport.For gills of A. californiensis, Ca²⁺ and Mg²⁺ losses are increased by 10^?3M 2,4-D relative to that into distilled water. Primary amine losses are increased for both A. californiensis and M. californianus gills at low 2,4-D concentrations.For A. californiensis and M. californianus gills the uptake of both 2,4-D and PNP are reduced by increasing concentrations of Ca²⁺ and Mg²⁺. In the case of A. californiensis, Ca²⁺ has a larger effect than Mg²⁺, which is consistent with the demonstrated stabilizing effect of Ca²⁺ on biological membranes. The uptake of PNP is larger than that of 2,4-D and glycine for gills of A. californiensis. The uptake of 2,4-D is reduced by the presence of an excess concentration of glycine but this is probably a physical effect. The uptake of 2,4-D, PNP, and glycine are all passive processes for A. californiensis gills. Glycine does not reduce 2,4-D uptake into M. californianus gills. For M. californianus the transport mechanism for glycine is not the same as that for 2,4-D; the former being active transport and the latter passive transport. However, 2,4-D does interfer with the active transport of glycine.     

Evaluation of two controlled-release 2,4-D formulations for control of Myviophyllum spicatum L.*

The controlled release herbicide delivery system 2,4-dichlorophenoxy-acetic acid/poly(glycidyl methacrylate) was evaluated for control of Myriophyllum spicatum L. Release profiles were constructed for the release of 2,4-dichlorophenoxy-acetic acid (2,4-D) from two polymer formulations into a reconstituted fresh water (pH 8). Herbicide was released with rates averaging 1.2 and 4.0 mg 2,4-D g-1polymer day-1 over the 112-day experiment, depending on the molecular weight of the glycidyl methacrylate precursors used in the preparation of the formulation. A formulation evaluated in a flowing water apparatus was effective for control of M. spicatum when treatment of the polymer was made with amounts calculated to maintain a herbicide concentration in the water of 0.08 mg 1^?1 or higher. The same 2,4-D polymer treated at 88 kg ae ha^?1 provided extended control of M. spicatum in a 5-month study in replicated outdoor pools with water flow adjusted to provide one volume change every 24 h. Evaluation de 2 formulations de 2,4-D à libération progressive pour la lutte contre Myriophyllum spicatum L. Le mécanisme de libération progressive du poly-(glycidyl methacrylate) acide 2,4-dichlorophen-oxyacétique a étéévalué dans le cadre de la lutte contre‘Myriophyllum spicatum L'. Des profils de libération ont étéétablis à partir de la libération de l'acide 2,4-dichlorophenoxyacétique (2,4-D) à partir de deux formulations polymerisées en suspension aqueuse (pH 8). L'herbicide était libéré avec des taux atteignant 1,2 et 4 mg de 2,4-D/gramme de polymère/jour pendant les 112 jours de l'expérimentation, en relation avec le poids moléculaire des précurseurs du glycidyl methacrylate utilisé pour la préparation de la formulation. Une formulation testée avec un appareil à courant d'eau s'est révélée efficace pour détruire M. spicatum quand le traitement était fait avec des quantités telles que soit maintenue une concentration d'au moins 0,08 mg/d'herbicide/litre d'eau. Le même 2,4-D polymérisé, appliquéà 88 kg/ha a permis une destruction prolongée de M. spicatum pendant les 5 mois de l'étude dans des bassins extérieurs avec un courant d'eau ajusté pour assurer un changement de volume par 24 heures. Untersuchung von zwei 2,4-D-Formulierungen mit kontrollierter Wirkstofffreisetzung zur Bekämpfung von Ähren-Tausendblatt (Myriophyllum spicalum L.) Die kontrollierte Wirkstofffreisetzung von 2,4-Dichlorphenoxyessigsäure aus Polyglycid-meth-acrylsäureester-Formulierungen wurde bei der Bekämpfung von Myriophyllum spicatum untersucht. Der Wirkstoff wurde dabei aus 2 Formulierungen mit unterschiedlichen Polymeren in Frischwasser (pH = 8) mit 1,2 und 4,0 mg 2,4-D g^?1 Polymer pro Tag während der Versuchsdauer von 112 Tagen freigesetzt. Die jeweilige Menge hing vom Molekulargewicht des in den Formulierungen eingesetzten Methacrylsäureesters ab, um in dem Durchfluss-System eine Herbizidkonzentration von mindestens 0,08 mg 1^?1 zur Bekämpfung der Pflanzen zu gewährleisten. Mit denselben 2,4-D-Formulierungen konnte in Freilandbecken (mit einmaligem Wasseraustausch innerhalb 24 Stunden) Myriophyllum spicatum mit 88 kg AS ha-1 bekämpft werden (Versuchsdauer: 5 Monate: mit Wiederholung).     

Effects of certain herbicides on the oxidative decarboxylation of tryptophan by peroxidase

Non-enzymic and peroxidase-catalysed oxidative decarboxylations of tryptophan (TPP) were studied. The in-vitro rate of enzymic reaction was affected by various herbicides at low concentrations (10^?5?10^?4_M): dinoseb, 2,4-D, dichlobenil and benazolin acted as inhibitors; on the other hand, chlorpropham, bromacil, diphenamid and 4-ethylamino-6-isopropylamino-1,3,5-triazin-2-ol (hydroxyatrazine) were stimulatory. The results of in-vivo experiments showed that chlorpropham and 2,4-D changed the activity of peroxidase from Brassica germinated seeds in vivo, as they do in vttro. Determinations of consumed TPP were carried out either by spectro-photometry or by chromatography.     

Concentration-Dependent Mobility of Chlorfenvinphos in Isolated Plant Cuticles

The mobility of chlorfenvinphos in isolated pear (Pyrus communis cv. Bartlett) leaf cuticular membranes (CM) was studied as a function of concentration of chlorfenvinphos sorbed in the cuticle. Mobilities of chlorfenvinphos increased approximately 9-fold when the amount sorbed increased from 1 to 100 μg cm⁻² pear leaf cuticle. From the amounts per area, average volume fractions of chlorfenvinphos in the cuticle were calculated ranging from 2×10⁻³ to 5·1×10⁻². The increase in mobilities was steepest at the lower and levelled off at higher volume fractions. This correlation could be described for the whole range of volume fractions investigated by an equation which assumes homogeneously dispersed chlorfenvinphos. Temperature dependence of mobilities was studied at 17, 25 and 35°C and chlorfenvinphos volume fractions of 5·5×10⁻³ and 0·12, respectively. Arrhenius graphs were linear for both volume fractions, showing that cuticles did not undergo a phase transition due to the high amount of sorbed chlorfenvinphos. However, at a volume fraction of 0·12, the activation energy of diffusion, E_D, was significantly lower (83·6 kJ mol⁻¹) than at 5·5×10⁻³ (135 kJ mol⁻¹). We interpret these findings as evidence for a plasticising effect on cuticular waxes by chlorfenvinphos. So far, such an effect had been demonstrated only for certain adjuvants (ethoxylated alcohols) but not for active ingredients. Chlorfenvinphos not only increased its own mobility in pear leaf cuticles, but also that of 2,4-D in Citrus leaf cuticles. This would be expected if plasticising of waxes was the sole mechanism responsible for increased mobilities. From these data we predict that permeabilities of cuticles to chlorfenvinphos are not constant. Depending on temperature as well as types and amounts of adjuvants, rates of foliar penetration of chlorfenvinphos can be higher if its concentration in the spray liquid is increased.     

基于表面引发原子转移自由基聚合技术制备2,4-二氯苯氧乙酸分子印迹聚合物及其识别特性分析

首次以氯甲基化交联聚苯乙烯树脂(CMCPS)为载体和大分子引发剂、2,4-二氯苯氧乙酸(2,4-D)为模板、丙烯酰胺(AM)为单体、乙二醇二甲基丙烯酸酯(EDMA)为交联剂、溴化铜/2,2'-联吡啶(CuBr/Bpy)为催化剂,采用表面引发原子转移自由基聚合(SI-ATRP)技术,制备了2,4-二氯苯氧乙酸分子印迹聚合物(2,4-D MIPs),并研究了模板分子与功能单体比例对该印迹聚合物吸附量的影响。通过动态、静态及竞争试验考察了该印迹聚合物对2,4-D的吸附性能。结果表明:2,4-D MIPs对模板分子2,4-D具有良好的特异性识别作用;与2,4-二氯苯酚和2,4-二氯苯甲醛相比,2,4-D MIPs对2,4-D的选择性系数分别为2.84和3.75,相对选择性系数分别为2.31和2.29。采用Scatchard模型分析,可以得到两类结合位点,计算得到最大表观吸附量(Qmax)分别为76.92和142.91 mg/g,离解常数Kd分别为632.91和2 309.47 mg/L。将2,4-D MIPs作为固相萃取剂,对豆芽样品进行添加回收试验,回收率为86%~104%,相对标准偏差(RSD)为1.9%~10%,方法的检出限为20 ng/g。该印迹聚合物可以富集分离测定2,4-D,稳定性好,并且能重复使用。