Uptake and movement of paraquat in cocksfoot and wheat as influenced by surfactants

Surfactants are used to increase the efficiency of herbicide formulations mainly because they wet out leaf surfaces, thereby stabilising and increasing the contact area of droplets on the surface. Herbicide penetration through the cuticle may also be facilitated. The work described eliminates effects on wetting and contact area in order to study the effect of surfactants on the penetration and movement of paraquat in cocksfoot. Surfactants were various types of alcohols and amine oxides condensed with 2 to 30 moles of ethylene oxide used at 0.1 to 0.5%. An adult leaf of cocksfoot (Dactylis glomerata) was immersed briefly to constant area in paraquat solutions containing surfactant and uptake and movement of paraquat is recorded. Uptake was little affected by differences in surfactant structure except where surface activity was low and solutions failed to wet out the leaf surface. Percentage movement with 0.5% surfactant was often less than that with 0.1% and a high ethylene oxide content also reduced percentage movement. Paraquat activity was influenced by both the degree of uptake and movement, but movement was the greater influence. Amine oxide surfactants reduced movement less than those based on alcohols. The action of surfactants is discussed in terms of a hydrophobic/hydrophilic balance in the surfactant molecule.     

Some physicochemical factors influencing foliar uptake enhancement of glyphosatemono(isopropylammonium) by polyoxyethylene surfactants

Structure-concentration–foliar uptake enhancement relationships between commercial polyoxyethylene primary aliphatic alcohol (A), nonylphenol (NP), primary aliphatic amine (AM) surfactants and the herbicide glyphosatemono(isopropylammonium) were studied in experiments with wheat (Triticum aestivum L.) and field bean (Vicia faba L.) plants growing under controlled-environment conditions. Candidate surfactants had mean molar ethylene oxide (EO) contents ranging from 5 to 20 and were added at concentrations varying from 0·2 to 10 g litre^?-1 to [¹⁴C]glyphosate formulations in acetone–water. Rates and total amounts of herbicide uptake from c. 0·2–μl droplet applications of formulations to leaves were influenced by surfactant EO content, surfactant hydrophobe composition, surfactant concentration, glyphosate concentration and plant species, in a complex manner. Surfactant effects were most pronounced at 0·5 g acid equivalent (a.e.) glyphosate litre^?-1 where, for both target species, surfactants of high EO content (15–20) were most effective at enhancing herbicide uptake: surfactants of lower EO content (5–10) frequently reduced, or failed to improve, glyphosate absorption. Whereas, at optimal EO content, AM surfactants caused greatest uptake enhancement on wheat, A surfactants gave the best overall performance on field bean; NP surfactants were generally the least efficient class of adjuvants on both species. Threshold concentrations of surfactants needed to increase glyphosate uptake were much higher in field bean than wheat (c. 2 g litre^?-1 and < 1 g litre^?-1, respectively); less herbicide was taken up by both species at high AM surfactant concentrations. At 5 and 10 g a.e. glyphosate litre^?-1, there were substantial increases in herbicide absorption and surfactant addition could cause effects on uptake that were different from those observed at lower herbicide doses. In particular, the influence of EO content on glyphosate uptake was now much less marked in both species, especially with AM surfactants. The fundamental importance of glyphosate concentration for its uptake was further emphasised by experiments using formulations with constant a.i./surfactant weight ratios. Any increased foliar penetration resulting from inclusion of surfactants in 0·5 g litre^?-1 [¹⁴C]glyphosate formulations gave concomitant increases in the amounts of radiolabel that were translocated away from the site of application. At these low herbicide doses, translocation of absorbed [¹⁴C]glyphosate in wheat was c. twice that in field bean; surfactant addition to the formulation did not increase the proportion transported in wheat but substantially enhanced it in field bean.     

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.     

The uptake of surfactants into wheat

The time course of uptake has been determined for seven poly(oxyethylene) surfactants, and one anionic surfactant (sodium dodecyl sulphate), into the leaves of wheat plants grown in a phytotron. Uptake was relatively rapid during an initial period of 24 h for six of the eight surfactants; after this period, the uptake rate was lower, and total uptake after 48 h was in the range 80-91% for those six surfactants. The other two compounds, sodium dodecyl sulphate and cetostearyl alcohol-22EO condensate (hexadecan-1-ol/octadecan-1-ol ethylene oxide condensate; average number of ethylene oxide units 22) were barely taken up at all. The observed time course for uptake was consistent with a complex process based on more than one rate-determining process. The physical properties of the surfactants are discussed in relation to their observed uptake behaviour. The surfactant deposit areas, measured by microscopy, were concluded to be not particularly relevant in interpreting the uptake results. Uptake was not related to surfactant chain length, but the physical form of the hydrated surfactant on a leaf surface appeared to influence uptake behaviour.     

Sorption of low levels of nonionic and anionic surfactants on soil: effects on sorption of triticonazole fungicide

The sorption of two anionic surfactants and a series of seven nonionic alkylphenolethoxylate surfactants of increasing hydrophilic/lipophilic balance (HLB) in a loamy clay soil was evaluated. The effect of low doses of these surfactants on the sorption characteristics of the fungicide triticonazole was investigated. The critical micellar concentration (CMC) of the surfactants in pure water and soil–water systems, and surfactant sorption were estimated by surface tension measurements using a batch equilibration technique. Triticonazole sorption, alone and in the presence of low doses of surfactants, was also measured by batch equilibration. CMC of the alkylphenol surfactants increased with their HLB. The sorption of surfactants increased with their lipophilicity. CMC in the soil–water systems were considerably higher than in pure water. Sorption of the most lipophilic alkylphenol surfactants at the higher doses significantly increased triticonazole sorption. Proposed mechanisms are modifications of soil surface properties, and increase of soil organic carbon content. Sorption of the other nonionic and anionic surfactants only resulted in monomeric surfactant concentrations in pore water, and did not affect triticonazole sorption. © 1998 Society of Chemical Industry     

Effect of some ethoxylated alkylphenols and ethoxylated alcohols on the transfer of [14C] chlorotoluron across isolated plant cuticles

The effect of several ethoxylated octylphenols (OP), nonylphenols (NP) and alcohols (AA) on the penetration of [¹⁴C]chlorotoluron through isolated box-tree (Buxus sempervirens L.) leaf cuticles was investigated. The herbicide solution was deposited as droplets onto cuticle discs maintained on agar blocks acting as receivers. The effects on chlorotoluron transfer across the cuticles depended on the degree of ethoxylation of the surfactant. For each series, the chlorotoluron transfer was considerably increased by surfactants with low ethylene oxide (EO) content (3 to 6 EO). This effect appeared 24 h after droplet application, then increased with time. It decreased with further increase in the ethoxylation number, and surfactants with a long ethylene oxide chain (OP16, NP20, NP40 and AA20) had no effect. Surfactant concentration (OP5) had a large influence on chlorotoluron transfer; penetration increased sevenfold when OP5 concentration was raised from 0.01 to 10 g l^?1. Diffusion of the two tritiated octylphenols, [3H]OP5 and [3H]OP16, was measured simultaneously during chlorotoluron transfer. The diffusion rate of the two surfactants across the cuticles was similar, but a higher amount of OP5 was retained within the cuticle during transfer. Study of the effect of surfactants on the cuticular waxes using differential scanning calorimetry showed that wax begins to melt at a lower temperature in the presence of the nonylphenols NP9 and NP4. Fusion enthalpy was close to -30 J g^?1. Effet de quelques alkylphénols et alcools éthoxylés sur la pénétration du [¹⁴C]chlortoluron à travers des cuticules végétales isolées Nous avons testé l'effet de plusieurs octylphénols (OP), nonylphénols (NP) et alcools éthoxylés (AA) sur la pénétration du [¹⁴C]chlortoluron à travers des cuticules isolées de feuilles de buis. L'herbicide en solution était déposé sous forme de gouttelettes sur des disques de cuticules plaées sur agar. Les effets observés dépendaient du degré d'ethoxylation du surfactant. Pour chaque série, le transfert du chlortoluron à travers les cuticules était considérablement accru avec les surfactants faiblement éthoxylés (3 à 6 oxydes d'éthylène). Cet effet apparaissait 24 h après l'application des gouttelettes puis augmentait avec le temps. Il diminuait avec l'accroissement du nombre d'éthoxylation et aucun effet n'était observé avec les surfactants à longue chaine d'oxydes d'éthylène (OP16, NP20, NP40 et AA20). La concentration en surfactant (OP5) avait une grande influence sur le transfert du chlortoluron dans l'agar, il augmentait sept fois entre 0.01 et 10 g l^?1. La diffusion des deux octylphénols (³H-OP5 et ³H-OP16) a été mesurée simultanément durant le transfert du chlortoluron. La vitesse de diffusion des deux surfactants à travers les cuticules était comparable, mais une quantité plus élevée d'OP5 était retenue dans les cuticules durant le transfert. L'étude par analyse calorimètrique à balayage de l'effet des surfactants sur les cires cuticulaires a montré que la fusion des cires commence à plus faible température en présence des nonylphénols NP9 et NP4. L'enthalpie de fusion était en général voisine de -30 J g^?1. Wirkung einiger ethoxylierter Alkylphenole und Alkohole auf den Transfer von [¹⁴C]Chlortoluron durch die Pflanzen-Cuticula Die Wirkung verschiedener ethoxylierter Octylphenole (OP), Nonylphenole (NP) und Alkohole (AA) auf die Penetration von [¹⁴C]Chlortoluron durch die isolierte Blatt-Cuticula von Buxbaum (Buxus sempervirens L.) wurde untersucht. Die Herbizidlösung wurde als Tröpfchen auf Cuticula-Scheiben, die auf Agarblöcken als Empfänger ausgelegt worden waren, ausgebracht. Die Wirkung auf den Chlortoluron-Transfer durch die Cuticula hing von der Ethoxylierung des Zusatzstoffes ab. In allen Serien wurde der Transfer durch Zusatzstoffe mit niedrigem Gehalt an Ethyloxiden (EO) erheblich gesteigert (3 bis 6 EO). Diese Wirkung trat 24 h nach der Applikation der Tröpfchen ein und nahm dann mit der Zeit zu. Mit dem Anstieg der Ethoxylierungszahl nahm die Wirkung ab, und Zusatzstoffe mit einer langen Ethylenoxidkette (OP16, NP20, NP40 und AA20) waren wirkungslos. Die Konzentration des OP5-Zusatzstoffes hatte großen Einfluß auf den Chlortolurontransfer; die Penetration war versiebenfacht, wenn die OP5-Konzentration von 0,01 auf 10 g l^?1 angehoben wurde. Die Diffusion der Octylphenole [³H]OP5 und [³H]OP16 wurde während des Chlortolurontransfers gemessen; die Diffusionsrate war ähnlich, aber von OP5 wurde ein größerer Anteil in der Cuticula zuückgehalten. Die Wirkung der Zusatzstoffe auf das Cuticularwachs wurde calorimetrisch untersucht, und es zeigte sich, daß das Wachs in Gegenwart der Nonylphenole NP9 und NP4 bei niedriger Temperatur zu schmelzen beginnt. Die Fusionsenthalpie lag bei -30 J g^?1     

Influence of surfactants on the leaching of bentazone in a sandy loam soil

BACKGROUND: Surfactants are very often used for more efficient pesticide spraying, but knowledge about their influence on the leaching potential for pesticides is very limited. In the present study, the leaching of the herbicide bentazone [3‐isopropyl‐1H‐2, 1,3‐benzothiadiazin‐4(3H)‐one 2,2‐dioxide] was measured in columns with sandy loam soil with or without the addition of a non‐ionic surfactant, octylphenol ethylene oxide condensate (Triton X‐100, Triton), and an anionic surfactant, sodium dodecylbenzenesulfonate (SDBS), and in the presence of both surfactants (SDBS + Triton). RESULTS: The mobility of bentazone (B) increased in the following order: B + Triton (slowest) < B + SDBS + Triton < B < B + SDBS (fastest). When Triton X‐100 was applied to the soil together with bentazone, the leaching of bentazone in the soil decreased significantly compared with leaching of bentazone without the addition of surfactant. SDBS and Triton X‐100 neutralised their influence on the leaching speed of bentazone in the soil columns when both surfactants were applied with bentazone. CONCLUSION: From the study it can be concluded that, depending on their properties, surfactants can enhance or reduce the mobility of bentazone. By choosing a non‐ionic surfactant, bentazone mobility can be reduced, giving time for degradation and thereby reducing the risk of groundwater pollution. Copyright © 2009 Society of Chemical Industry     

Bacterial biodegradation of ethoxylated surfactants

Agricultural, industrial and domestic use of surfactants leads to the entry of these compounds into terrestrial and aquatic ecosystems. Synthetic surfactants vary significantly in structure, but most consist of alkyl or alkylphenol groups attached to nonionic or anionic hydrophilic moieties. Continued use of these compounds is usually justified on the basis that they do not cause pollution problems because they undergo biodegradation by micro-organisms present in soils and surface waters. In accomplishing biodegradation, micro-organisms, predominantly bacteria, are exploiting these potentially useful resources of reduced carbon to derive energy and support growth in situations which are otherwise frequently oligotrophic. This paper reviews aspects of surfactant biodegradation, especially in relation to alcohol and alkylphenol ethoxylates used extensively as adjuvants for agrochemicals. In principle, bacteria can employ two strategies to gain access to the aliphatic chains in alcohol ethoxylate surfactants: separation of the hydrophobic chain from the hydrophile (central fission), or direct attack on the -terminal of the alkyl chain of the intact surfactant. Direct exo-cleavage of ethylene glycol units from the polyethylene glycol (PEG) chain also provides a third route to assimilable carbon. In pure cultures of known degraders or in mined environmental samples, all three strategies are exploited, some even within the same organism. Central fission occurs predominantly at the alkyl-ether bond, but may also occur within the PEG chain itself, thus producing various glycol intermediates which accumulate in pure cultures but appear only transiently in mixed environmental samples. Against this background, the relative resistance of some alkylphenol ethoxylates to biodegradation can be assessed in mechanistic terms. The steric bulk of the aryl nucleus effectively eliminates the central fission pathway. Moreover, some alkyl phenol ethoxylates contain branched alkyl chains which restrict ω-β-oxidation. As a result, ethoxylate shortening appears to be the major course of biodegradation observed so far. Not surprisingly, these surfactants are observed to undergo extensive primary biodegradation (removal of surfactant properties) but relatively restricted ultimate degradation to carbon dioxide and normal cell components.     

A review of the effects of humidity, humectants, and surfactant composition on the absorption and efficacy of highly water-soluble herbicides

It is well known that environmental conditions have an important influence on herbicide efficacy. In particular, the effect of humidity on herbicide uptake has been attributed to changes in cuticle hydration and droplet drying. As early as the 1950s, it was hypothesized that humectants such as glycerol would enhance herbicide uptake by not letting droplets dry, thus maintaining the herbicide in solution, and hence making it available for uptake. Shortly thereafter, evidence was found to support this hypothesis and humectants were used successfully in warm, dry areas to increase herbicide efficacy. However, by the mid-1980s, there was little use of humectants as research on humectants gave way to investigations on the effect of ethylene oxide (EO) content on surfactant performance to improve herbicide uptake and efficacy. While ethoxylated surfactants effectively increase the uptake of both lipophilic and hydrophilic herbicides, the suggestion that long EO chains have humectant properties is misleading, since the studies that led to this suggestion were performed at high humidity, which would prevent rapid droplet drying. Furthermore, current evidence suggests that highly water-soluble, ionic herbicides may be more sensitive to low humidity and rapid drop drying than lipophilic herbicides. Therefore, an overview is presented on the interaction of water-soluble herbicides with surfactants, the cuticle, and humidity, with particular emphasis on the impact of low humidity and humectants on herbicide uptake. It was found that when one focuses on research performed at low humidity the importance of humectants emerges, which is not in keeping with what is now commonly accepted.     

Increased foliar activity of clodinafop‐propargyl and/or tribenuron‐methyl by surfactants and their synergistic action on wild oat (Avena ludoviciana) and wild mustard (Sinapis arvensis)

Surfactants can improve postemergence herbicide efficacy and reduce the amount of herbicide required to obtain weed control. The effect of surfactants on the efficacy of herbicides is complicated and depends on the interaction among the plant, surfactant, and herbicide. The effects of surfactants on the efficacy of clodinafop‐propargyl and/or tribenuron‐methyl on wild oat (Avena ludoviciana) and wild mustard (Sinapis arvensis) under greenhouse conditions were investigated. In addition, the surface tension of aqueous solutions of the surfactants and surfactants + herbicides was determined. Significantly lower surface tension values were obtained with the aqueous solutions of citofrigate (Citogate plus Frigate) alone and with the herbicides used in this study. The citofrigate surfactant lead to the greatest enhancement of clodinafop‐propargyl and/or tribenuron‐methyl efficacy and the effect was species‐dependent. The efficacy of clodinafop‐propargyl and/or tribenuron‐methyl in the presence of surfactants in controlling wild oat was higher than for wild mustard. The foliar activity of the tested herbicides rose with increasing surfactant concentrations. The tank mixture of clodinafop‐propargyl and tribenuron‐methyl showed a synergistic effect in controlling wild oat and wild mustard. The synergistic effect in controlling wild mustard was greater than for wild oat.     

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.     

Surfactants and the uptake and movement of paraquat in plants

Surfactants are still considered to be agents which either increase spray coverage of leaves with herbicidal solutions and/or increase herbicide penetration into the leaves. Experiments where the method of application largely eliminates leaf wetting as a factor in paraquat uptake show that this is an over-simplification. Its efficiency in the plant is influenced by penetration and most of all by the degree of movement down the plant into untreated leaves. Results on the uptake, movement and biological activity of paraquat are reported using cocksfoot and wheat. A relation is found between paraquat movement and the hydrophilic nature of the surfactant. It moves most when the number of ethylene oxide residues is less than six and it is minimal when the number is 10 to 15. Leaf penetration, however, is at a maximum when movement under the influence of surfactant is least. Partition studies in which surfactants are distributed between leaf wax and water are described. There is a direct correlation between the degree of partition of the surfactant into the wax and the degree of movement of paraquat in cocksfoot and wheat. Surfactants are essential components of a paraquat formulation to wet the leaf surface and increase penetration but, when the surfactant also penetrates into the leaf, it reduces the mobility of paraquat and hence its efficiency.     

Ultrastructural effects of formulated picloram on leaflets of velvet mesquite and catclaw acacia*

The effects of picloram formulated with a nonionic surfactant (X-77) and of the surfactant alone on the ultrastructure of leaf cells of velvet mesquite (Prosopis velutina Woot.) and catclaw [Acacia greggii var. ariznica (Gray) Isely] were examined The surfactant induced temporary protrusions from chloroplasts in both species. A proliferation of rough endoplasmic reticulum (RER) was noted in velvet mesquite within 8h of application of the herbicide and in catclaw with in 27 h. By 72h after treatment. both species exhibited distortions of organelles with more severe symptoms in catclaw. the species more sensitive to the herbicide Leaf abscission occurred subsequently and was more pronounced in catclaw than in mesquite_l It is known that RER proliferation is induced by ethylene and that ethylene evolution is stimulated by picloram. The present study suggests that the interaction between these two chemicals was similar in the two plant species studied.     

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.     

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.     

Physiological investigations into the resistance of a wild mustard (Sinapis arvensis L.) biotype to auxinic herbicides

Possible mechanism(s) of resistance to auxinic herbicides in wild mustard (Sinapis arvensis L.) were investigated by characterizing responses of susceptible and resistant biotypes to 2,4-D, di-camba or picloram. No differences between bio-types were observed in absorption, translocation, or metabolism of foliar-applied radiolabelled herbicides. In contrast, the levels of ethylene production varied between biotypes. The susceptible biotype produced twofold and sixfold more ethylene than the resistant biotype within 4 h and 44 h of herbicide application, respectively. These results suggest that the mechanism of resistance in wild mustard is not due to differences in absorption, translocation, or metabolism. Ethylene production studies imply that resistance to auxinic herbicides may be attributed to altered target site(s) of action. Bases physiologiques de la résistance aux herbicides auxiniques d'un biotype de moutarde des champs (Sinapis arvensis L.) Les mécanismes possibles de la résistance aux herbicides auxiniques chez la moutarde des champs (Sinapis arvensis L.) ont été recherchés en caractérisant les réponses de biotypes résis-tants et sensibles au 2,4-D, au dicamba et au pi-clorame. Aprés application des herbicides radioactifs sur le feuillage, aucune différence d'absorption, de migration ou de métabolisme n'a été observée. Par contre, la production d'éthylene différait entre les biotypes. Le biotype sensible produisait 2 et 6 fois plus d'éthylène que le biotype sensible, respectivement 4 et 44 heures après l'application d'herbicide. Ces résultats sug-gèrent que la résistance aux herbicides auxiniques chez la moutarde des champs n'est pas due à des différences d'absorption, de migration ou de métabolisme mais pourrait provenir d'une altération du site d'action. Physiologische Untersuchung der Resistenz eines Acker-Senf-(Sinapis arvensis-) Biotyps gegenüber Wuchsstoffherbiziden Der mögliche Mechanismus der Resistenz gegenüber Wuchsstoffherbiziden beim Acker-Senf (Sinapis arvensis L.) wurde unhand der Reaktion von empfindlichen und resistenten Biotypen gegenüber 2,4-D, Dicamba oder Picloram untersucht. Hinsichtlich Absorption, Translokation oder Metabolismus der auf die Blätter applizierten, radioaktiv markierten Her-bizide wurden keine Unterschiede beobachtet. Die Ethylenbildung variierte jedoch zwischen den Biotypen. Der empfindliche produzierte in-nerhalb 4 oder 44 Stunden nach der Herbizid-applikation 2-bzw. 6mal mehr Ethylen als der resistente. Aus den Ergebnissen läßt sich schließen, daß beim Acker-Senf der Resisten-zmechanismus nicht in der Absorption, der Translokation oder dem Metabolismus liegt, sondern die Ethylenbildung daran beteiligt ist, wo die Wirkorte fur die Wuchsstoffherbizide liegen.     

Effects of adjuvants on the performance of a novel powdery mildew fungicide, 1-(4-chlorobenzyl)-4-phenylpiperidine

The effects of adjuvants on the performance of a dispersible concentrate formulation (DCI) of a novel powdery mildew fungicide, 1-(4-chlorobenzyl)-4-phenylpiperidine (I) were investigated. The method involved assessment, under glasshouse conditions, of the therapeutic (curative) control of infections of powdery mildew (Erysiphe graminis DC f.sp. hordei Marchal) on barley (Hordeum vulgare, L.) eight to nine days after spray application to plants that had been inoculated one day prior to spraying. The results from the first trial showed that marked improvements (∽five-fold) in the performance of DCI could be obtained by the spray tank addition of some types of surfactant adjuvants and a series of further trials investigating a wide range of adjuvants was conducted. Nonylphenol, alkylamine and alcohol ethoxylates varying in mean ethylene oxide content between 5 and 20 moles were highly effective. There were indications that optimum performance enhancements were obtained with these surfactants containing between 5 and 10 moles ethylene oxide. Lower enhancements, sometimes only marginal, were obtained from trisiloxane, phosphate ester, propylene oxide, alkylamine-propylene oxide and castor oil ethoxylates and also alkyl polyglucoside biosurfactants. Negligible adjuvant enhancements were observed with emulsifiable paraffinic/naphthenic and rape seed oils, though slightly better enhancements were seen with an emulsifiable transmethylated rape seed oil and, interestingly, larger enhancements with an emulsifiable lipophilic alcohol. A final trial identified the alcohol ethoxylate, ‘Dobanol’ 91-6, as the most effective adjuvant and that its optimum application rate under glasshouse conditions was 250 g ha^-1. This information will be used to guide the design of field trials. © 1997 SCI     

Herbicidal control of Cirsium arvense (L.) Scop,roots and shoots in no-till spring wheat (Triticum aestivum L.)*

Three herbicide treatments were applied each year over a period of 4 years to Cirsium arvense (L.) Scop, infestations in no-till spring wheat (Triticum aestivum L.) in North Dakota, USA. Both chlorsulfuron at 30 g ai ha^?1+a non-ionic surfactant and a mixture of clopyralid+2,4-D at 70+280 g ai ha^?1 gradually reduced Cirsium arvense shoot density, root biomass, and adventitious root buds over the 4-year treatment period in two trials. These two treatments did not merely induce adventitious root buds to become dormant. They virtually eliminated roots to a depth of 50 cm by year 4. Tribenuron methyl at 10 g ai ha^?1+ a non-ionic surfactant was less effective in reducing shoot density and root biomass. Lutte herbicide contre les racines et les tiges de Cirsium arvense (L.) Scop, dans du bli de printemps non laboure (Triticum aestivum L.) Trois traitements herbicides ont été appliqués chaque année pendant 4 ans, contre des infestations de Cirsium arvense (L.) Scop, dans du blé de printemps (Triticum aestivum L.) non labouré dans le Dakota Nord, USA. Tant le chlorsulfuron à 30 g m.a. ha^?+un surfactant nonionique qu'un mélange de clopyralide+2,4-D à 70+280 g m.a. h^? ont reduit progres-sivement la densité des pieds de Cirsium arvense, la biomasse racinaire, et les bourgeons racinaires adventices pendant les 4 années de traitements dans les 2 essais. Ces traitements ont à peu près éliminé les racines sur une profondeur de 50 cm en 4 ans. Ces deux traitements n'ont pas induit de dormance des bourgeons racinaires adventices. Le tribenuron methyl à 10 g m.a. ha^?+un surfactant non ionique a été moins efficace dans la réduction de la densité de plante et de la biomasse racinaire. Chemische Bekämpfung von Cirsium arvense (L.) Scop, in direktgesätem Sommerweizen (Triticum aestivum L.) In direktgesäter Sommerweizen (Triticum aestivum L.) wurdel in North Dakota. USA, Bestände von Cirsium arvense (L.) Scop, über 4 Jahre jährlich 3 Herbizidbehandlungen unterzogen. Sowohl Chlorsulfuron mit 30 g AS ha^?1 nichtionischem Netzmittel als auch eine Mischung von Clopyralid+2,4D mit 70+280 g AS ha^?1 verringerten die Sproßdichte der Acker-Kratzdistel, die Wurzelbiomasse und die Adventivknospen an den Wurzeln in 2 Ver-suchen graduell. Durch diese beiden Behand-lungen wurden nicht nur die Adventivknospen dormant, sondem auch die Wurzeln bis zu einer Tiefe von 50 cm bis zum 4. Jahr fast ganz elimi-niert. Tribenuron-methyl mit 10 g AS ha^?1 nichtionischem Netzmittel war hinsichtlich der Reduktion von Sproßdichte und Wurzelbiomasse weniger wirksam.     

Crop weed competition and herbicide performance in cereal species and varieties

In dose-response experiments with the herbicide combinations MCPA+dichlorprop and ioxynil+mecoprop in barley, winter wheat, and winter rye varieties, oilseed rape (Brassica napus L.) was used as a substitute for weeds. The results showed a significant interaction between the competitive ability of varieties and herbicide performance. A negative exponential model with variety as categorical variable was used to analyse the data and to assess the competitive effect of the varieties on herbicide efficacy. A target level of 5 g weed dry matter m^?2 in all varieties at the end of flowering was used to derive a varietal calibration factor of the herbicide dose. The results showed significant differences in calibration factors between species of winter wheat, barley, and rye, and between varieties of spring barley and winter wheat. In the winter wheat variety Sleipner it was necessary to use a 154% higher herbicide dose than in the winter barley variety Trixi, whereas in the winter rye variety Petkus II, herbicide dose could be reduced by 31% compared with Trixi. The differences between spring barley varieties were smallerbut significant. Competition entre culture et mauvaises herbes, et efficacité herbicide chez différentes espèces et variétés de céréales Dans des expériences dose-effet avec les combinaisons herbicides MCPA+dichlorprop et ioxynil+mécoprop dans différentes variétés d'orge, de blé d'hiver et de seigle d'hiver, le colza (Brassica napus L.) était utilisé comme modèle de mauvaise herbe. Les résultats ont montré une interaction significative entre l'aptitude à la concurrence des variétés et l'efficacité herbicide. Un modèle exponentiel négatif avec la variété comme variable catégorielle, a été utilisé pour analyser les données et pour déterminer l'effet de l'aptitude à la compétition des variétés sur l'efficacité herbicide. Un objectif de 5 g de matière sèche de mauvaise herbe par m² pour toutes les variétés à la fin de la floraison a été utilisé pour déterminer un facteur de calibration varietal de la dose d'herbicide. Les résultats ont montré des différences significatives entre les facteurs de calibration déterminés pour les espèces blé d'hiver, orge et seigle, ainsi qu'entre les variétés d'orge de printemps et de blé d'hiver. Avec la variété de blé d'hiver Sleipner, U était nécessaire d'utiliser une dose d'herbicide supérieure de 154%à celle nécessaire pour la variété d'orge d'hiver Trixi, alors que dans le seigle d'hiver Petkus II, la dose herbicide pouvait ßtre réduite de 31 % par rapport à Trixi. Les différences entre variétés d'orge de printemps étaient plus faibles mais significatives. Konkurrenz zwischen Kulturpflanzen und Unkraut und Herbizidwirkung bei Getreidearten und -Sorten In Dosis-Wirkungs-Untersuchungen mit den Herbiziden MCPA+Dichlorprop und loxynil+Mecoprop wurde in Gersten-, Winterweizen- und Winterroggensorten Raps (Brassica napus L.) als Unkraut eingesetzt. Die Ergebnisse zeigten eine signifikante Wechselwirkung zwischen der Konkurrenzkraft von Sorten und der Herbizidwirkung. Ein negativ exponentielles Modell mil der Sorte als Kategorie wurde angewandt, um die Da ten zu analysieren und den Einfluß der Sorten auf die Herbizidwirksamkeit zubestimmen. Es wurde eine Zielgröße von 5 gm^?2 Unkrauttrockenmasse in allen Sorten zum Endeder Blüte gesetzt, um einen sortenbezogenen Kalibrierungsfakt or für die Herbiziddosis zu erhalten. Es wurden signifikante Unterschiede der Kalibrierungsfaktoren zwischen den Getreidarten Winterweizen, Gerste und Roggen und zwischen den Sommergersten- und Winterweizensorten gefunden. Bei der Winterweizensorte Sleipner war es erforderlich, eine 154 % höhere Herbiziddosis als bei der Wintergerstensorte Trixi anzuwenden, während die Herbiziddosis bei der Winterroggensorte Petkus II im Vergleich zu Trixi um 31 % reduziert werden konnte. Die Unterschiede waren bei Sommergerstensorten geringer, jedoch signifikant.     

The activity and mobility of triasulfuron in soil as influenced by organic matter,duration, amount and frequency of rain

The influence of different levels of organic matter and of the duration, amount and frequency of rainfall on the biological activity and mobility of triasulfuron were investigated. Biological activity was inversely related to the organic matter content of the soil. Movement of the herbicide down the soil profile, assessed by bioassay, was inversely related to the organic matter content of the soil, and the amount and frequency of rain directly influenced the extent of leaching of the herbicide. Triasulfuron was moved to a depth of at least 22.5 cm when soil columns were exposed to a total of 528 mm of natural rainfall over a period of 6 months. The presence of phytotoxic levels of the herbicide in the surface layers of soil columns 6 months after exposure to outdoor temperatures and natural rainfall suggested that triasulfuron may persist in soils for relatively long periods. Influence de la matiére organique, et de la durée, niveau et fréquence des précipitations sur l'activité et la mobilité du triasulfuron dans le sol L'influence de différentes teneurs en matière organique et de la durée, quantité et fréquence des pluies sur l'activité biologique et la mobilité du triasulfuron a étéétudiée. L'activité biologique est inversement liée avec la teneur enmatière organique du sol. Le mouvement descendant de l'herbicide dans le profil du sol, estimé par bio essai, est inversement lié avec la teneur en matière organique du sol, et la quantité et la fréquence des pluies influencent directement l'importance de la lixiviation de l'herbicide. Le triasulfuron s'est déplacé jusqu'à une profondeur d'au moins 22,5 cm quand les colonnes de sols ont été exposées à un total de 52,8 cm de pluies naturelles sur une période de 6 mois. La présence de taux phytotoxiques d'herbicide dans les couches superficielles des colonnes de sol 6 mois après l'exposition aux températures extérieures et aux précipitations naturelles montre que le triasulfuron peut persister dans 1s sols pendant des périodes relativement longues. Einfluβ der organischen Substanz des Bodens sowie der Niederschlagsdauer, -menge und -frequenz auf Persistenz und Mobilität von Triasulfuron im Boden Die biologische Aktivität sowie die Verlagerung von Triasulfuron im Boden, mit Biotests bestimmt, waren umgekehrt proportional zum Gehalt an organischer Substanz. Die Regenmenge sowie -frequenz beeinflußten die Einwaschung des Herbizids direkt. Bei insgesamt 528 mm natürlichem Niederschlag innerhalb 6 Monaten wurde Triasulfuron in Bodensäulen mindestens 22,5 cm tief eingewaschen. Aus dem Vorhandensein phytotoxischer Mengen des Wirkstoffs in den oberen Schichten der Bodensäulen nach 6 Monaten unter Freilandbedingungen wurde auf relativ hohe Persistenz im Boden geschlossen.