Cuticular uptake of xenobiotics into living plants. Part 2: influence of the xenobiotic dose on the uptake of bentazone, epoxiconazole and pyraclostrobin, applied in the presence of various surfactants, into Chenopodium album, Sinapis alba and Triticum aestivum leaves

This study has determined the uptake of three pesticides, applied as commercial or model formulations in the presence of a wide range of surfactants, into the leaves of three plant species (bentazone into Chenopodium album L. and Sinapis alba L., epoxiconazole and pyraclostrobin into Triticum aestivum L.). The results have confirmed previous findings that the initial dose (nmol mm(-2)) of xenobiotic applied to plant foliage is a strong, positive determinant of uptake. This held true for all the pesticide formulations studied, although surfactant concentration was found to have an effect. The lower surfactant concentrations studied showed an inferior relationship between the amount of xenobiotic applied and uptake. High molecular mass surfactants also produced much lower uptake than expected from the dose uptake equations in specific situations.     

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.     

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.     

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.     

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.     

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.     

Factors affecting the foliar absorption and redistribution of pesticides. 1. Properties of leaf surfaces and their interactions with spray droplets

Foliar uptake into eleven plant species, grown under controlled environment, has been determined for spray deposits of glyphosate, 2, 4-D and prochloraz applied as solutions in aqueous solvents in the presence and absence of an ethoxylated nonylphenol surfactant. Over 24 h, uptake of glyphosate did not exceed 6% of applied chemical into any species whereas uptake of 2, 4-D and prochloraz differed between species and was modified significantly by the addition of surfactant. Uptake of prochloraz was increased consistently by adding surfactant, but the response of 2, 4-D was variable. Increased uptake was attributed mainly to surfactant-enhanced wetting of the leaf surfaces. Uptake of prochloraz per unit wetted area increased in the presence of surfactant but that of 2, 4-D decreased. Uptake of either chemical did not correlate with the presence of specialised leaf surface structures, cuticular morphology or distribution of the chemicals within the dried deposits. The dried chemicals were distributed either uniformly or as annuli as a result of complex interactions between the active ingredient, surfactant and the leaf surfaces. Regression analysis indicated that the epicuticular wax and cuticular membrane were the major sinks for both 2, 4-D and prochloraz during the 24-h period.     

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.     

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 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.     

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.     

Surfactant-enhanced foliar uptake of some organic compounds: Interactions with two model polyoxyethylene aliphatic alcohols

Interactions occurring during the surfactant-enhanced foliar uptake of seven model organic compounds were examined using two homogeneous surfactants, hexaethylene glycol monotridecyl ether (C13E6) and hexadecaethylene glycol monododecyl ether (C12E16). Surfactant–compound and compound–surfactant interactions were detected by measurement of their relative uptake rates following application of c. 0·2 μl droplets of the corresponding radiolabelled formulations. The magnitude of surfactant–compound interaction was found to vary according to the physicochemical properties of both the compound and the surfactant, and was influenced by surfactant concentration and target plant species. Interactive and non-interactive mechanisms, both leading to substantial enhancement of compound uptake, could be identified, but their precise nature could not be elucidated. Although penetration of C13E6 into the site of application appeared to be essential in order to activate the uptake of a compound, substantial absorption of C12E16 was not always required to produce the same effect. The results are discussed in the light of possible sites and modes of action for activator polyoxyethylene surfactant adjuvants.     

Effect of additives in aqueous formulation on the foliar uptake of dimethomorph by cucumbers

BACKGROUND: The efficacy enhancement of dimethomorph formulation by several adjuvants is thought to be through increased foliar uptake. In order to identify the most effective adjuvants, the adjuvancy of 36 additives was examined in aqueous formulations in relation to the absorption of dimethomorph by cucumber leaves. RESULTS: Polyethylene glycol monohexadecyl ethers with ethylene oxide (EO) contents of between 7 and 20, polyethylene glycol monooctadecyl ethers with EO contents of between 10 and 20 and polyethylene glycol monooctadecenyl ethers with EO contents of between 6 and 20 were effective adjuvants for promoting dimethomorph uptake from both aqueous acetone solutions and aqueous wettable powder (WP) suspensions into cucumber leaves. Polyethylene glycol monododecyl ethers with EO contents of between 7 and 9 were effective in promoting dimethomorph uptake from aqueous WP suspensions but less effective relative to the other adjuvants tested with aqueous acetone solutions. Foliar uptake of dimethomorph was also facilitated by the addition of methyl hexadecanoate, methyl octadecenoate and methyl octadecadienoate. CONCLUSIONS: Although the foliar uptake of dimethomorph from both aqueous WP suspensions and aqueous acetone solutions was greatest in the presence of fatty alcohol ethoxylates generally having a C₁₆ or C₁₈ lipophile, uptake from aqueous surfactant–acetone solutions was, on average, 7.6‐fold greater than that from aqueous WP suspensions containing surfactant. Copyright © 2009 Society of Chemical Industry     

Visualization of the effect of a surfactant on the uptake of xenobiotics into plant foliage by confocal laser scanning microscopy

A radiolabelling method is generally used to determine the foliar uptake of xenobiotics. This technique cannot provide any information on the localization of chemicals inside leaf tissues. The influence of an alcohol ethoxylate surfactant on the uptake of three fluorescent dyes, difluorofluorescein (hydrophilic), rhodamine B (moderately lipophilic) and a naphthalimide dye (lipophilic), into the leaves of three contrasting species, bean (Vicia faba), wheat (Triticum aestivum) and cabbage (Brassica oleracea), at 16 h after treatment was measured using a conventional wash‐off method and also visualized in vivo by confocal laser scanning microscopy (CLSM). Whereas the lipophilic dyes showed greater intrinsic uptake than the hydrophilic one, the enhancing effect of the surfactant on uptake was more pronounced for the latter. CLSM revealed that the presence of the surfactant increased the transport of difluorofluorescein into the epidermal cells of bean and wheat leaves, but not cabbage leaves. Rhodamine B showed greatest transcuticular diffusion in all three species, but most of the dye moved into the vacuole of the epidermal cells. The naphthalimide dye was strongly retained by the wax–cuticle layer of all species, even in the presence of the surfactant. CLSM has proven to be an attractive tool for studying xenobiotic diffusion. The results obtained using fluorescent dyes are believed to be applicable to the foliar uptake of herbicides.     

Uptake and translocation of non-ionised pesticides in the emergent aquatic plant parrot feather Myriophyllum aquaticum

The uptake of four (14)C-labelled non-ionised compounds, the methyl carbamoyloxime insecticide/nematicide oxamyl and three model phenylureas, from solution by rooted stems of the aquatic plant parrot feather [Myriophyllum aquaticum (Vell.) Verdc], together with translocation to the emergent shoots, was measured over periods of 24 and 48 h. Uptake into the submerged tissues of roots and stem base could be ascribed to two processes: movement into the aqueous phase of cells and then partitioning onto the plant solids. This latter process was related to lipophilicity (as measured by the l-octanol/water partition coefficient, K(ow)) and gave rise to high uptake rates of the most lipophilic compounds. Translocation to shoots was passive and was optimal at log K(ow) approximately 1.8, at which the efficiency of translocation of compound was about 40% of that of water. This optimum log K(ow) was identical to that observed previously in barley, although the translocation efficiency was somewhat less in parrot feather. Solvation parameters were applied to model uptake and translocation of a set of ten compounds by barley with the particular objective of understanding why translocation efficiency is lower at log K(ow) > 1.8.     

Foliar uptake of pesticides—Present status and future challenge

Uptake of pesticides into plant foliage varies with plants and chemicals, and can be greatly influenced by adjuvants and environmental conditions. It is known that the penetration of pesticides into plant leaves is related to the physicochemical properties of the active ingredients, especially molecular size and lipophilicity. However, the uptake rate of a compound cannot be predicted by either of them or even combination of them. For a specific chemical, uptake varies greatly with plant species and there is no simple method at the moment to quickly evaluate the leaf surface permeability of a plant. Various adjuvants are being used to increase the penetration of pesticides into target plant foliage, but their effects vary with chemicals and plant species. The mechanisms of action of adjuvants in enhancing pesticide uptake remain unclear despite the effort made during the last three decades. Modern analytical and microscopic techniques provide powerful tools to deepen our understanding in this field. However, a more multidisciplinary approach is urgently needed to elucidate the transcuticular diffusion behaviour of pesticides and the mode of action of adjuvants. A better understanding of the foliar uptake process should lead to a more rational use of pesticides and minimize their negative impact on the environment.     

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.     

Adjuvants and herbicidal efficacy – present status and future prospects

The influence of adjuvants on spray liquid behaviour and herbicide performance is reviewed. Total formulation efficacy can be expressed as a function of [deposition:retention:uptake: translocation:a.i. toxicity]. Adjuvants influence the physico-chemical and plant interactions involved for each factor. Deposition efficiency of spray droplets on to a target is dependent largely on the droplet spectrum, whereas retention performance is dependent on plant leaf surface character, orientation and canopy architecture, as well as droplet volume, velocity and dynamic surface tension effects. Uptake into plant foliage is affected by the leaf surface wax, cuticle age and composition and species variability. Uptake can be improved through appropriate formulation to provide either stomatal infiltration or much greater and faster cuticular absorption of the active ingredient. The inherent translocation capability of the a.i. is not affected directly by adjuvants, which are relatively immobile, but they can increase the mass of absorbed a.i. translocated, as a consequence of improved uptake or may reduce it as a result of localized contact phytotoxicity. Considerable progress has been made in developing models of spray droplet deposition, adhesion and retention, as well as uptake. In future, individual models may be combined to provide an integrated formulation efficacy decision support system.     

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.     

Relevance of the deposit structure for the uptake and bio-efficacy of diquat,as monitored by the spatially resolved chlorophyll fluorescence

Aim of our study was to exploit the relation between deposit structure at the microscale and the uptake and biological efficacy of herbicides. For this purpose, we analysed the relevance of the deposit structure of diquat dibromide, as affected by surfactants, on the spatially resolved chlorophyll fluorescence (ChlF) and the desiccation of the leaves. The present study is a sequential work to our studies with the systemic compound glyphosate. On that basis, we hypothesized here that larger deposits of diquat are negatively related to the bio-efficacy of the compound. By using selected ethoxylated rapeseed oil adjuvants (RSO 5, RSO 10, RSO 30, RSO 60) we influenced the deposit properties of diquat dibromide droplet residue on the leaves of easy-to-wet Viola arvensis and the difficult-to-wet Chenopodium album species. With the spatially-resolved pulse amplitude modulated (PAM) ChlF technique we demonstrated the effect of diquat on the physiology of the tissue. As shown, the RSO surfactants did not affect the area of diquat residue on the easy-to-wet leaves of V. arvensis; this trend is similar to those observed for ChlF and the herbicide desiccation potential. In contrary, on C. album, decreased deposit area of diquat droplet was associated with increased effect on ChlF parameters and increased desiccation potential of the herbicide, thus explaining its higher foliar uptake.