Contributions of stomatal infiltration and cuticular penetration to enhancements of foliar uptake by surfactants

Radiolabelled deoxyglucose (DOG) and glyphosate were used to investigate the effects of certain non-ionic surfactants on the kinetics of foliar uptake in three species. ‘Silwet L-77’ (5 g litre^?1), an organosilicone surfactant, enabled spray solutions to infiltrate stomata, providing uptake of DOG into Vicia bean (50%), oat (35%) and wheat (20%) within 10 min of application. ‘Silwet Y-12301’, another organosilicone, also induced stomatal infiltration but to a lesser extent; unlike L-77, this was attenuated by partial stomatal closure. A third organosilicone, ‘Silwet L-7607’, and two conventional surfactants, ‘Triton X-45’ (OP5) and ‘Agral 90’ (NP9), did not induce stomatal infiltration. The effective minimum concentration of L-77 required to enable infiltration of stomata was 2 g litre^?1. The uptake of glyphosate into bean did not differ from that of DOG but the ‘Roundup’ formulation of glyphosate partially antagonised the infiltration provided by L-77. Addition of surfactants did not increase the rate of cuticular penetration of DOG into bean but total uptake was increased, except by NP9, either via infiltration (L-77 and Y-12301) or by extending the period during which penetration occurred (L-7607 and OP5). The surfactants had a variable effect on rates of penetration of DOG into wheat and oat. In general, foliar uptake followed an exponential timecourse which was largely complete within 6 h and only rarely approached 100% of the applied chemical. The stomatal infiltration provided by L-77 caused an increase in translocation of DOG in bean.     

Effects of some nonionic polyoxyethylene surfactants on uptake of ethirimol and diclobutrazol from suspension formulations applied to wheat leaves

The influence of a number of commercial nonionic polyoxyethylene surfactants on the foliar penetration and movement of two systemic fungicides, ethirimol and diclobutrazol, was studied in outdoor-grown wheat plants at different growth stages and post-treatment temperatures in two consecutive growing seasons. Both fungicides were applied as ca 0·2 μl droplets of aqueous suspension formulations containing 0·5 g litre^?1 of ¹⁴C-labelled active ingredient; surfactants were added to these suspensions at concentrations ranging from 0·2-10 g litre^?1. To achieve optimum uptake of each fungicide the use of surfactants with different physicochemical properties was required. For diclobutrazol, a lipophilic compound, uptake of radiolabel was best with surfactants of low mean molar ethylene oxide (E) content (5-6) but it was necessary to use concentrations of ca 5 g litre^?1 to attain this. The surfactant threshold concentration for uptake enhancement of radiolabel from ethirimol formulations (< 2 g litre^?1) was much lower than that for diclobutrazol but surfactants with E contents > 10 induced the greatest amount of uptake. For both fungicides, surfactants with an aliphatic alcohol hydrophobe were generally more efficient in promoting their uptake than those with a nonylphenol moiety. The sorbitan-based surfactant ‘Tween 20’ proved to be an effective adjuvant only for the ethirimol formulation; the uptake enhancing properties of the block copolymer ‘Synperonic PE/F68’ were weak. Uptake performance could not be related to the spreading properties of the respective formulations on the wheat leaf surface or to differences in solubilisation of the two fungicides by the surfactants. Although surfactants could substantially increase the amount of acropetal transport of radiolabel from both fungicides, none of those tested specifically promoted it; a constant proportion of the radioactive dose absorbed by a treated leaf was usually exported away from the site of application. The results are discussed in the light of current theories about the mode of action of surfactants as spray adjuvants.     

Development of a predictive uptake model to rationalise selection of polyoxyethylene surfactant adjuvants for foliage-applied agrochemicals

Composition-concentration relationships between a series of C₁₃/C₁₄ polyoxyethylene primary alcohol (AE) surfactants and the foliar uptake enhancement of five model neutral organic compounds were examined in factorially designed experiments on wheat (Triticum aestivum L.) and field bean (Vicia faba L.) plants grown under controlled environment conditions. Model compounds were applied to leaves as c.0.2-μl droplets of 0.5 g litre^?1 solutions in aqueous acetone in the absence or presence of surfactants at 0.2, 1 and 5g litre^?1. Uptake of the highly water-soluble compound, methylglucose (log octanol-water partition coefficient (P) = - 3.0) was best enhanced by surfactants with high E (ethylene oxide) contents (AE15, AE20), whereas those of the lipophilic compounds, WL110547 (log P = 3.5) and permethrin (log P = 6.5), were increased more by surfactants of lower E contents, especially AE6. However, there was little difference between AE6, AE11, AE15 and AE20 in their ability to promote uptake of the two model compounds of intermediate polarity, phenylurea (log P = 0.8) and cyanazine (log P = 2.1). Absolute amounts of compound uptake were also influenced strongly by both surfactant concentration and plant species. Greatest amounts of uptake enhancement were often observed at high surfactant concentration (5 g litre^?1) and on the waxy wheat leaves compared with the less waxy field bean leaves. The latter needed higher surfactant thresholds to produce significant improvements in uptake. Data from our experiments were used to construct a simple response surface model relating uptake enhancement to the E content of the surfactant added and to the physicochemical properties of the compound to be taken up. Qualitative predictions from this model might be useful in rationalising the design of agrochemical formulations.     

Influence of some nonionic surfactants on water sorption by isolated tomato fruit cuticles in relation to cuticular penetration of glyphosate

The effects of several nonionic surfactants on [¹⁴C]glyphosate mono(isopropylammonium) diffusion across isolated tomato fruit cuticles (Lycopersicon esculentum Mill.) were compared under controlled atmospheric conditions (25°C; 65% R.H.) using a model system consisting of 1-μl droplets applied to isolated cuticles on agar blocks. Rates of diffusion for glyphosate (10 g acid equivalent litre^?1 in the applied solution) and overall amounts recovered in underlying agar blocks were influenced by the ethylene oxide (EO) chain length for a homologous nonylphenol surfactant series (10 g litre^?1). Glyphosate uptake increased with EO content, reaching an optimum at a mean of 17 EO, then decreasing below control values for surfactants with 40 EO. There was a strong influence of the hydrophobe on glyphosate penetration for different surfactants with similar mean EO content (10 EO). The primary aliphatic amine enhanced penetration the most, followed by the nonylphenol while the aliphatic alcohol showed no improvement on glyphosate transfer across cuticles. Water soprtion was greatly enhanced by a primary aliphatic amine (10 EO) and by a nonylphenol (17 EO). The aliphatic alcohol (10 EO) and a shorter-chained nonylphenol (4 EO) did not significantly enhance water sorption. Comparison of water sorption with glyphosate diffusion across cuticles suggests a strong relationship between the two. Change in solution pH over a limited range had no significant effect. Promotion of cuticular hydration by surfactants may thus play an important role in the enhancement of foliar uptake of water-soluble herbicides such as glyphosate.     

Surfactant and salt affect glyphosate retention and absorption

The influence of nonylphenoxy surfactants and glyphosate salt formulation on spray retention, phytotoxicity and [¹⁴C]glyphosate uptake was investigated in wheat (Triticum aestivum L). and Kochia scoparia L. The amount of spray retained, and uptake of [¹⁴C]glyphosate increased with increasing hydrophilic-lipophilic balance (HLB) value of surfactants. The volume of spray delivered to the plant treatment area and retained by wheat and K. scoparia plants increased with increasing surfactant HLB values, but this only partly accounted for the higher spray retention. Spray retention by leaves of plants was not affected by calcium chloride, either alone or with ammonium sulphate in the glyphosate spray solution. [¹⁴C]Glyphosate absorption by wheat and K. scoparia was reduced by calcium chloride alone, but not in mixtures with ammonium sulphate, regardless of surfactant. Phytotoxicity and uptake of glyphosate salt formulations for wheat was: isopropylamine > ammonium > sodium > calcium; these results indicate that the surfactant selected is important to maintain glyphosate efficacy and that sodium and calcium cations antagonize glyphosate by forming salts that are absorbed less than commercial isopropylamine formulations.     

Effect of non-ionic nonylphenol surfactants on surface physicochemical properties, uptake and distribution of asulam and diflufenican

The effect of non-ionic nonylphenol (NP) surfactants containing 4–14 ethylene oxide (EO) molecules on the distribution of asulam and diflufenican was investigated in Pteridium aquilinum L. Kuhn and Avena fatua L. The distribution of the herbicides was dependent on the EO content and concentration of surfactant and differed between plant species and herbicide. The surface properties of contact angle, droplet diameter and surface tension were examined. For solutions of asulam, the greatest reductions in contact angle, surface tension and greatest droplet diameter were obtained with surfactants of EO 6.5–10 (at 0.001–0.1%). For solutions of diflufenican, these responses were greatest when applied with surfactant of EO 4. Surfactants of EO 6.5–10 increased the uptake and translocation of [¹⁴C]asulam in P. aquilinum, particularly at surfactant concentrations of 0.01 % and 0.1 %. All surfactants increased uptake of [¹⁴C]asulam in A. fatua with no significant effects of surfactant EO number or concentration. For both species, there was a positive correlation between the optimum surface characteristics of the herbicide droplets and the uptake of asulam. With diflufenican, greatest uptake and translocation by mature frond tissue of P. aquilinum occurred at the highest concentration of surfactant EO 4; in A. fatua, however, uptake and translocation were not significantly affected by any of the surfactants.     

Studies on octylphenoxy surfactants. Part 2: Effects on foliar uptake and translocation

The effects of octylphenol (OP) and four of its ethoxylated derivatives on uptake into, and distribution within, maize leaf of 2-deoxy-glucose (2D-glucose), atrazine and o, p′-DDT are reported. The surfactants and OP (2 g litre^?1 in aqueous acetone) increased the uptake, at both 1.5 and 24 h, of the three model compounds (applied at 1 g litre^?1) having water solubilities in the g, mg and μg litre^?1 ranges. The uptake of 2D-glucose was positively correlated with the hygroscopicity of the surfactants. The uptake of DDT and atrazine increased with the uptake of the surfactants, being inversely related to their hydrophile:lipophile balance (HLB). Uptake of 2D-glucose and atrazine was enhanced at high humidity, the relative enhancement for atrazine increasing with increasing ethylene oxide (EO) content of the surfactants. A significant proportion of the atrazine and DDT entering the leaf was recovered from the epicuticular wax, the amount of atrazine recovered from the wax increasing with the EO content of the surfactants. The proportion of the surfactants taken up which was recovered from the epicuticular wax was minimal at an EO content of 12.5–16 mole equivalents. The appearance of the deposits on the leaf surface differed markedly among the surfactants, with similar trends for all three chemicals and without visible evidence for infiltration of the stomatal pores. The total quantities of glucose and atrazine translocated were increased by all surfactants but that of DDT was not, despite increases in uptake of up to 7.5-fold. Relative translocation (export from treated region of leaf as a percentage of chemical penetrating beyond the epicuticular wax) was reduced in all cases in the presence of surfactant. Up to 30% of the applied [¹⁴C]chemicals was not recovered from the treated leaf after 24 h. The reduced recovery of 2D-glucose, but not that of atrazine and DDT, was largely attributable to movement out of the treated leaf, with approximately 70% of the chemical taken up being translocated basipetally. Loss of atrazine and DDT was a result of volatilisation. There was no evidence that either [14C]2 D-glucose or [¹⁴C]atrazine was metabolised to [¹⁴C]carbon dioxide.     

Effects of surfactants and the kinetic energy of monodroplets on the deposit structure of glyphosate at the micro‐scale and their relevance to herbicide bio‐efficacy on selected weed species

The deposit pattern of foliar‐applied agrochemicals, and its relation to their bio‐efficacy, has major practical importance. Thus, in our experiments, we evaluated the relevance of the deposition properties of glyphosate for its bio‐efficacy. The deposition pattern of glyphosate monodroplets was influenced by using surfactant and by applying the droplets with or without kinetic energy to the plant foliage. Monodroplets (1 μL) of glyphosate, formulated with or without ethoxylated rapeseed oil surfactant (RSO) having on average 5, 10, 30 or 60 ethylene oxide units (EO), as well as one commercial glyphosate product (CGP), were applied either by carefully placing the droplet on the foliage with a pipette (kinetic energy assumed to be near zero) or by a monodroplet generator (with kinetic energy). We selected two easy‐to‐wet (Stellaria media and Viola arvensis) and two difficult‐to‐wet (Chenopodium album and Setaria viridis) weed species as target plants. The deposit structure was determined using a scanning electron microscope with energy dispersive x‐ray microanalysis. The kinetic energy of the droplet had no consistent effect on the deposit structure or the bio‐efficacy of glyphosate formulations. In contrast, surfactants differing in EO unit, affected both the deposit structure and the bio‐efficacy of the formulations, depending upon the species. In easy‐to‐wet species, the increase in EO unit of RSO surfactant failed to affect the deposit area of glyphosate and its bio‐efficacy. However, in difficult‐to‐wet species, the increase in EO unit of RSO surfactant reduced the deposit area of glyphosate and enhanced its bio‐efficacy.     

Effects of formulation with different adjuvants on foliar uptake of difenzoquat and 2,4-D: model experiments with wild oat and field bean

The effect of different adjuvants on the foliar uptake of difenzoquat methyl sulfate and sodium 2,4-D was studied in wild oat and field bean plants growing under controlled environmental conditions. The ¹⁴C-herbicides were applied to leaves as c. 0–2-μl droplets, usually containing 0.5 g 1^?1 active ingredient, plus adjuvants in the range 0.05–5 g 1^?1. The addition of non-ionic polyoxyethylene surfactants to solutions of both herbicides could induce considerable foliar uptake. Aliphatic C₁₃C₁₃ alcohol surfactants generally improved uptake more than nonylphenol surfactants when used at equivalent concentrations and ethylene oxide (EO) contents. The surfactant threshold for enhancement of difenzoquat uptake in wild oat was very low (0.05 g 1^?1), whilst that in field bean was much higher (>0.5 g 1^?1). For 2,4-D, surfactants at >0–5 g 1^?1 were needed to produce substantial increases in its uptake into both species. Although surfactants of low EO content (5–6) were less efficient at promoting difenzoquat uptake than those of higher EO content (10–20), particularly in wild oat, there was little dependence on surfactant EO content for enhancement of 2,4-D uptake. Adjuvants with humectant properties also promoted penetration of difenzoquat, but less so than alcohol or nonylphenol surfactants. For formulations of both ¹⁴C-herbicides translocation was directly related to the quantity of radiolabel that had penetrated the leaf tissue. Effets de la formulation avec différents adjuvants sur l'absorption foliaire du difenzoquat et du 2,4-D: modeles experimentaux sur la folle avoine et le haricot L'influence de differents adjuvants sur l'absorption foliaire du difenzoquat methyl sulfate et du 2,4 D sodium a eétéétudiée chez la folle avoine et le haricot, cultivés sous des conditions environnementales contrôlées. Les herbicides marquees au ¹⁴C ont ete appliquées aux feuilles sous forme de gouttelettes de 0,2 μl contenant 0,5 g 1^?1 de matière active, avec en plus des adjuvants de 0,05 à 5 g ^?1. L'adjonction de surfactants polyoxyethylénes non ioniques aux solutions des deux herbicides pourrait induire un absorption foliaire importante. Les surfactants d'alcools aliphatiques C₁₃/C₁₅ ont généralement augmenté la pénétration mieux que les surfactants de type nonylphénol utilises à une concentration équivalente et que les oxydes d'éthylènes (EO). Le seuil de surfactant pour l'amélioration de l'absorption de difenzoquat sur folle avoine était très bas (0,05 g 1^?1) tandis que sur haricot, il était beaucoup plus éievé (> 0,5 g 1^?1). Pour le 2,4 D, des surfactants à une dose de >0,5 g 1^?1 sont nécessaires pour produire une amelioration de son absorption chez les deux espéces. Bien que les surfactants à faible teneur en EO (5–6) fussent moins efficace pour favoriser l'absorption du difenzoquat que ceux a forte teneur (10–20), spécialement pour la folle avoine, il y avait une petite dépendance sur la teneur en EO pour l'amélioration de l'absorption du 2,4 D. Les adjuvants avec des propriétés d'humectation ont favorisé la pénétration du difenzoquat, mais moins que les surfactants alcool ou nonylphenol. Pour les formulations des deux herbicides marqués au ¹⁴C, le transport était directement reliéà la quantité de molécule marquée ayant pénétrée dans le tissu foliaire. Wirkung verschiedener Netzmittel auf die Blattaufnahme von Difenzoquat und 2,4-D am Beispiel von Flug-Hafer und Ackerbohne Der Einfluß verschiedener Zusatzstoffe auf die Blattaufnahme von Difenzoquat und 2,4-D-Na- Salz wurde an Flug-Hafer- und Ackerbohnen-Pflanzen unter kontroUierten Bedingungen untersucht. Die ¹⁴C-Herbizide wurden auf die Blatter mit etwa 0,2 μl großen Tröpfchen einer Lösung mit 0,5 g 1^?1 AS und 0,05 bis 5 g 1^?1 des Zusatzstoffs ausgebracht. Durch Zugabe von nichtionischen Polyoxyethylen-Netzmittein zu den Lösungen der beiden Herbizide konnte die Blattaufnahme erheblich gesteigert werden. Aliphatische C₁₃C₁₅-Alkohol-Netzmittel förderten die Aufnahme mehr als Nonylphenol-Netzmittel, wenn sie mit equivalenten Konzentrationen und Ethylenoxid-(EO)Gehalten ausgebracht wurden. Die Schwelle für die Steigerung der Difenzoquat-Aufnahme durch Netzmittel lag bei Flug-Hafer sehr niedrig (0,05 g 1^?1), bei der Ackerbohne vielhöher (>0,5 g 1^?1). Bei 2,4-D wurden bei beiden Arten zur deutlichen Förderung der Aufnahme Netzmittelkonzentrationen von >0,5 g 1^?1 benötigt. Obwohl Netzmittel mit niedrigem EO-Gehalt (5–6) die Difenzoquat-Aufnahme weniger förderten als solche mit höherem Gehalt (10–20). besonders bei Flug-Hafer, ergab sich für die Förderung der 2,4-D-Aufnahme kaum eine Abhängigkeit vom EO-Gehalt des Netzmittels. Additive mit feuchtigkeitshaltenden Eigenschaften förderten auch die Aufnahme von Difenzoquat, aber weniger als alkoholische oder nonylphenolische Netzmittel. Die Translokation der Mischungen der beiden ¹⁴C-Herbizide stand in direktem Verhäitnis zur Radioaktivitätsmenge, die in das Blattgewebe aufgenommen wurde.     

Uptake of aminotriazole from humectant-surfactant combinations and the influence of humidity

Uptake of aminotriazole (3-amino-1,2,4-triazole) by bean leaves (Phaseolus vulgaris var. Canadian Wonder) was not greatly influenced by the addition to the spray solution of dimethylformamide (DMF), ethylene glycol and polypropylene glycol 400 (PPG 400) over the concentration range 1.0–50.0 ml litre^?1. However, the addition of polyoxyethylene 20 sorbitan monolaurate (polysorbate 20) (0.2–1.0 g litre^?1) to spray solutions of the above additives and glycerol (5.0 ml litre^?1; except for DMF, 50.0 ml litre^?1) substantially increased uptake to 80–100% in all cases at 50 ± 10% relative humidity (r.h.). Similar penetration figures were recorded when a range of polysorbate surfactants (polysorbate 20, 40, 60, 80 and 85; 0.2 g litre^?1) were applied to spray solutions containing either dimethyl sulphoxide (DMSO) or glycerol (5.0 ml litre^?1). Humidity was found to have a critical effect upon the humectant-surfactant combinations tested, i.e. DMSO + polysorbate 20, ethylene glycol+ polysorbate 20 and PPG + 400-polysorbate 20 (5.0 ml litre^?1+0.2 g litre^?1). With DMSO + polysorbate 20 the following uptake figures were recorded: < 30% r.h., 3.1 %; 45 ± 10% r.h., 86.8%; 55–65% r.h., 48.2 % and 100% r.h., 0.3%. Similar trends were recorded with all three humectant-surfactant combinations. Further studies revealed that the adverse effect of humidity on DMSO-polysorbate mixtures could be at least overcome partially by regulating the DMSO concentration.     

Non-target effect of herbicides: I. effect of glyphosate and hexazinone on soil microbial activity. Microbial population,and in-vitro growth of ectomycorrhizal fungi

The effects of two herbicides, glyphosate (as a 359 g litre^?1 SL) and hexazinone (as a 50gkg^?1 granule) on soil microbial population, carbon dioxide evolution, and in-vitro growth of five species of ectomycorrhizal fungi were investigated. Glyphosate at 0–54 and 3.23 kg a.i. ha^?1 and hexazinone at 1. 2 and 8 kg a.i. ha^?1 did not reduce soil microbial population or carbon dioxide evolution in the long term (6 months). However, there was a significant short-term (2 months) effect of glyphosate on both fungal and bacterial counts at the 0.54 kg ha^?1 treatment. In in-vitro tests, Cenococcum graniforme. Hebeloma crustuliniforme and Laccaria laccata were more susceptible to both herbicides than was Suillus tomentosus. which was, in turn, more susceptible than Paxillus involutus. The growth of all five ectomycorrhizal fungi was significantly reduced when subjected to concentrations above 50 μl formulation litre^?1 (glyphosate) or 50 μg formulation litre^?1 (hexazinone).     

Relation between volatility rating and composition of phenoxy herbicide ester formulations

A CIPAC/AOAC test with tomato plants is used to specify the volatility ratings of herbicide ester formulations. This work compares the tomato plant test with an alternative chemical one. The concentrations of esters and the effective molecular weight and density of each formulation were used with the ester vapour pressures to calculate its herbicide vapour pressure as complete, and evaporated formulations. The range was from 28.8 mPa (at 257deg;C) for a mixture of 2,4–D esters to 0–07 mPa (at 25°C) for a 2,4,5–T-(iso-octyl) formulation, as complete formulations, and 35-5 and 0–16 mPa (at 25°C) as evaporated ones. A value of 0–6 mPa (at 25°C) was selected on the basis of the tomato plant test as the cut-off area for low-volatile esters and is recommended to be included in specifications for herbicide esters. Formulations with a herbicide vapour pressure above 3.3 mPa (at 25°C) are high-volatile ones according to the tomato plant test, while between 0–6–3.3 mPa (at 25°C) is a borderline region where the test gives mixed results. Levels of 2,4–D-ethyl and methyl were added to pure 2–ethylhexyl esters of 2,4–D and a 2,4,5–T-(iso-octyl) formulation to find what level of contamination would change the rating of these esters from low to high volatile. Formulations of 2,4–D-(iso-octyl) should not contain more than 11 g litre^?1 2,4–D as methyl ester or 2.0 g litre^?1 2,4–D as ethyl ester. Formulations of 2,4,5–T-(iso-octyl) should not contain more than 26 g litre^?1 2,4–D as methyl ester or 4.7g litre^?1 2,4–D as ethyl ester.     

Influence of wetting agents on the foliar uptake and herbicidal activity of glufosinate

The influence of four different wetting agents on the foliar retention, uptake and herbicidal activity of the glutamine synthetase inhibitor, glufosinate, was examined in growth-chamber experiments on barley (Hordeum vulgare L. cv Roland) and barnyard grass (Echinochloa crus-galli (L.) P.B.) as test species. The non-formulated monoammomum salt, glufosinate-ammonium, was applied as a spray, either alone or mixed with a wetting agent. The dose rates of herbicide and wetting agent were 0.5 g a.i. litre^?1 and 2.0 g litre^?1, respectively, on barnyard grass, and 2.0 g a.i. litre^?1 and 60 g litre^?1, respectively, on barley. Herbicide damage, rated 10 days after spraying, was greatest when glufosinate was used with a sodium C₁₂/C₁₄-alcohol-diglycolether sulfate (FAEO-sulfate) and least with polyoxyethylene (POE)(8) tridecyl ether; intermediate effectiveness was obtained with a combination of herbicide and a POE(15) tridecyl ether or POE(15)-tallow amine. The activity of the target enzyme, glutamine synthetase, measured 2 h after spraying, was reduced most when FAEO-sulfate was present and least with POE(8) tridecyl ether. The behaviour of the glufosinate wetting agent solutions on plant foliage was analysed by measurements of spray retention, droplet contact angles and foliar uptake of [¹⁴C]glufosinate. The results led, for both grass species, to the conclusion that differential ability of the wetting agents to enhance the permeation of glufosinate from the leaf surface deposit into the leaf tissue was the main factor responsible for the differences in herbicidal effectiveness of the glufosinate/wetting agent combinations used in this study.     

Promotion of stomatal infiltration of glyphosate by an organosilicone surfactant reduces the critical rainfall period

The addition of the organosilicone surfactant ‘Silwet L77’ at 1-5 ml litre^?1 to formulated glyphosate gave complete surface wetting on application to the adaxial leaf surface of perennial ryegrass (Lolium perenne L.). The wetting characteristics of the solution were associated with rapid foliar uptake and near maximal uptake in 3 h compared to greater than 5 h in the absence of ‘Silwet L77’. Evidence is presented showing that solutions containing ‘Silwet L77’ rapidly infiltrate stomata. Rapid uptake did not occur after application to the astomatous abaxial surface of perennial ryegrass leaves. The rapid rate of glyphosate uptake reduced the critical rainfall period to 2 h or less, compared to up to 10 h in the absence of ‘Silwet L77’. The use of ‘Silwet L77’ has major practical implications for the use of glyphosate in regions with unpredictable rainfall or high rainfall frequency.     

In-vivo evaluation of adjuvants for more effective control of celery leaf-spot (Septoria apiicola) and powdery mildew (Erysiphe graminis) of wheat with fungicides

The effects of seven adjuvants (at 0, 0.5, 1.0 and 2.0 g litre^?1) on the efficacies of four fungicides al 0.5 g litre^?1 were studied in the laboratory for the control of leaf-spot in celery (caused by Septoria apiicola) and powdery mildew on winter wheat (caused by Erysiphe graminis). The most effective fungicides for controlling leaf-spot were: tebuconazole + triadimenol = flutriafol > mancozeb + oxadixyl > prochloraz. However, addition of adjuvant to the fungicides gave a modified pattern of effectiveness. The efficacy of flutriafol was strongly enhanced by addition of all adjuvants, but those of prochloraz and mancozeb+oxadixyl only partially so. The tested adjuvants were mineral oil + surfactant, a polymer/alkoxylated alkyl ether blend, an ethoxylated alkylphenol, an ethoxylated hexitan ester blend, an ethoxylated nonylphenol and an alkylpolysaccharide- based adjuvant mixture. However, the addition of adjuvants to tebuconazole + triadimenol had a negative effect. Of all the adjuvants tested, the nonylphenol ethoxylate and a mixture of mineral oil /surfactant and alkylpolysaccharides gave the highest efficacy with the fungicides, while the mineral oil/surfactant and the alkylpolysaccharides alone were less effective. There was a positive relationship between high concentrations of adjuvants and their effectiveness, but there were some exceptions. The most effective fungicides for control of powdery mildew in wheat were prochloraz, mancozeb + oxadixyl and tebuconazole + triadimenol. There was a linear relationship between the high efficacy of the fungicide and the concentration of adjuvants to control powdery mildew in wheat. The highest concentration of adjuvant (2-0 g litre^?1) gave the highest efficacy for the fungicides.     

The algaecidal activity of some substituted 1,3-diphenylureas, 1-phenyl-3-(2-pyridyl)ureas and the corresponding thioureas

Twelve ureas and thioureas with 1,3-diphenyl- and 1-phenyl-3-(2-pyridyl) were tested as potential herbicides in a simple screen against two species of algae Chlorella fusca and Anabaena variabilis. Several were shown to inhibit growth at 100 mg litre^?1 but only 1-[2,4-bis(azidosulphonyl)phenyl]-3-(2-pyridyl)urea and 1,3-bis(4-isopropyl- idenehydrazinosulphonylphenyl)thiourea showed any activity at 1 mg litre^?1. This compares with the well-established urea herbicide diuron which, in identical tests, gives similar inhibition of growth at concentrations as low as 0.01 mg litre^?1.     

Effect of ABT on the activity and rate of degradation of isoproturon in susceptible and resistant biotypes of Phalaris minor and in wheat

The effect of the monooxygenase inhibitor, 1-aminobenzotriazole (ABT) on isoproturon phytotoxicity and metabolism was studied in resistant (R) and susceptible (S) biotypes of Phalaris minor and in wheat (Triticum aestivum). Addition of ABT (2·5, 5 and 10 mg litre^-1) to isoproturon (0·25, 0·5, 1, 2 and 4 mg litre^-1) in the nutrient solution significantly enhanced the phytotoxicity of isoproturon against the R biotype. Isoproturon at 0·25 mg litre^-1 reduced the dry weight (DW) of the S biotype by 77%, whereas the R biotype required 4·0 mg litre^-1 for similar reduction. Addition of 10 mg litre^-1 of ABT to the 0·25 mg litre^-1 isoproturon caused 71 and 82% reduction in DW of R and S biotypes, respectively. Wheat was more sensitive to the mixture of isoproturon and ABT than the R biotype of P. minor. Reduced concentrations of ABT in the mixture from 10 to 2·5 mg litre^-1 increased the DW of the R biotype more than that of the S biotype. The R biotype metabolised [¹⁴C]isoproturon at a faster rate than the S biotype. ABT (5 mg litre^-1) inhibited the degradation of [¹⁴C]isoproturon in both biotypes of P. minor and in wheat. In the presence of ABT, about half of the applied [¹⁴C]isoproturon remained as parent herbicide in all the three species after two days. The metabolites were similar in the R and S biotypes and wheat as determined by co-chromatography with reference standards and mass spectroscopy (MS). ABT inhibited the appearance of the hydroxy and monomethyl metabolites and their conjugates in all the test plants. These results suggest that the activity of the enzymes responsible for the degradation of isoproturon is greater in the R than in the S biotype of P. minor, resulting in its rapid detoxification. Incorporation of the monooxygenase inhibitor ABT into the nutrient solution greatly inhibited the degradation of [¹⁴C]isoproturon in the R biotype and increased its phytotoxicity. Both hydroxylation and N-dealkylation reactions were found to be sensitive to ABT; inhibition of hydroxylation was greater than that of demethylation. Since ABT could not completely suppress isoproturon degradation, it is possible that more than one monooxygenase is involved. © 1998 SCI     

A scanning electron microscope study of glyphosate deposits in relation to foliar uptake

The effects of several formulations on foliar uptake of glyphosate, and on the morphology of glyphosate deposits on leaves, were examined in Tartary buckwheat (Fagopyrum tataricum (L.) Gaertn.). [¹⁴C]glyphosate, in the form of the free acid or the isopropylamine salt (IPAS), was applied to foliage alone or with various adjuvants. Uptake of all glyphosate IPAS formulations was greater than that of the corresponding acid formulation. Addition of ‘Tween 20’ enhanced the uptake of glyphosate IPAS compared to glyphosate alone, but had no effect on the uptake of glyphosate acid. Ammonium sulfate and the ‘Roundup’ formulation blank increased the uptake of glyphosate acid and IPAS to 2-3 times that of herbicide alone. Surface deposits, as observed by scanning electron microscopy, varied with the formulation of the herbicide, although there were no differences between the acid and IPAS formulations. Glyphosate alone initially formed a deposit with both crystalline and smooth, amorphous areas. Later in the treatment period (48 and 72 h after application), the deposit was almost entirely crystalline. The addition of ‘Tween 20’ or of formulation blank resulted in the formation of a more amorphous, non-crystalline deposit. Herbicide solutions containing ammonium sulfate dried to form a highly crystalline deposit. However, crystals similar to those of glyphosate alone were not visible in these deposits. The ability of these adjuvants to prevent or delay crystal formation may play a role in their enhancement of herbicide uptake.     

Residues of the algicide endothal in water,soil and rice,after paddy field applications

In order to obtain residue data from the application of the algicide endothal in Italian rice paddy fields, two experiments were carried out using a 50 g kg^?1 granular formulation in a small pond and the same granular and two liquid formulations in actual paddy fields of the Italian rice growing area. Endothal decay in the pond water was very rapid, reaching residue levels of 0·01-1·02 mg litre^?1 in two days and 0·004-0·01 mg litre^?1 at the third day. The muddy soil of the pond was free from measurable endothal residues( <0·02 mg kg^?1). In the paddy-field waters, the endothal decay was slower, with an average half-life time of 3·3 days, independently of the type of formulation. The actual residues in water after 6 days ranged from 0·3 to 1·3 mg litre^?1 according to the initial amount of product applied, and, consequently, to the initial concentration in water. Rice samples collected at the normal harvest time from the two paddy fields, treated with three different formulations, showed no endothal residue at the minimum detectable level of 0·01 mg kg^?1.     

Basis for changes in glyphosate phytotoxicity to barley by the non-ionic surfactants Tween 20 and Renex 36*

The non-ionic surfactants, Tween 20 (polyoxy-ethylene 20 sorbitan monolaurate) and Renex 36 (polyoxyethylene 6-tridecyl ether) enhanced the retention of a glyphosate-dye spray solution by barley (Hordeum vulgare L.) leaves. Tween 20 also enhanced absorption of ¹⁴C-glyphosate applied as droplets to barley leaves whereas Renex 36 similarly applied, reduced both absorption and movement of ¹⁴C-glyphosate. Renex 36 alone or mixed with glyphosate increased leakage of electrolytes from barley leaf segments whereas neither Tween 20 nor glyphosate, alone or mixed together, had any effect. No ¹⁴C-glyphosate complexes were detected in mixtures with either surfactant and neither surfactant affected the pH of the glyphosate solution. The results indicate that the reported enhancement of glyphosate phytotoxicity by Tween 20 is due to increased retention and absorption of the herbicide while the reported antagonism caused by Renex 36 is due to reduced glyphosate absorption and movement possibly as a result of alteration of membrane integrity.