Modelling the effects of alcohol ethoxylates on diffusion of pesticides in the cuticular wax of Chenopodium album leaves

Cuticular waxes represent the first and, in most cases, the limiting barrier for foliar uptake of pesticides from solution. Sorption of pesticides in reconstituted cuticular wax (wax/water partition coefficients) of Chenopodium album L. and in isolated cuticular membranes (cuticle/water partition coefficients) of Prunus laurocerasus L. was determined. Diffusion coefficients of pesticides in reconstituted cuticular wax of C. album leaves were size-dependent, increasing with increasing molar volume. In the presence of alcohol ethoxylates, diffusion coefficients were enhanced by up to two orders of magnitude, and size selectivity was significantly decreased. The accelerating effect and the decrease in size selectivity were attributed to plasticisation of the cuticular wax by the alcohol ethoxylates increasing the fluidity in the wax. A free volume model adopted from polymer science was successfully applied to predict diffusion coefficients of pesticides on the basis of the transport properties of the wax (size selectivity and crystallinity), the molar volume of the diffusing compound and the accelerator concentration in the wax.     

Mobilities of Organic Compounds in Reconstituted Cuticular Wax of Barley Leaves: Effects of Monodisperse Alcohol Ethoxylates on Diffusion of Pentachlorophenol and Tetracosanoic Acid

Effects of monodisperse alcohol ethoxylates on mobilities of ¹⁴C-labelled pentachlorophenol (PCP) and tetracosanoic acid (C₂₄AC) in reconstituted cuticular wax of barley leaves were measured. Depending on the respective alcohol ethoxylate investigated, the diffusion coefficient (D) of PCP in barley wax was increased by factors ranging from 3·3 to 19·6, whereas D of C₂₄AC, was increased by factors varying between 22 and 315. In order to analyse the relationship between the concentration of surfactants in the wax and their effects on D, the amounts of alcohol ethoxylates dissolved in the wax at equilibrium with external concentrations well above the critical micelle concentration (CMC) were determined. Wax/water partition coefficients (K_ww) of the alcohol ethoxylates were about one order of magnitude lower than cuticle/water partition coefficients (K_cw), which is a consequence of the semi-crystalline structure of the wax compared with amorphous cutin. Correlations between effects on D and maximum amounts of alcohol ethoxylates dissolved in the wax were obtained indicating an unspecific wax/surfactant interaction. This was solely dependent on the amount of surfactant sorbed to the wax, leading to increased mobilities of pesticides in the wax. Applying ESR-spectroscopy, which gave an insight into the molecular structure of the wax, supported this interpretation of an unspecific plasticising effect of the alcohol ethoxylates on the molecular structure of the wax. The results obtained in this study are in good accordance with the results obtained in a recent study investigating the effects of the same group of alcohol ethoxylates on mobilities of pesticides in isolated, but intact, cuticular membranes of Citrus. This demonstrates that the investigation of isolated and subsequently reconstituted cuticular wax is a useful model system analysing the mechanisms of the surfactant interaction with the transport-limiting barrier of plant cuticles.     

Analysis of foliar uptake of pesticides in barley leaves: Role of epicuticular waxes and compartmentation

Uptake of pesticides into barley leaves was measured under controlled conditions. Leaves detached from plants were submerged in aqueous solutions of ¹⁴C-labelled (2,4-dichlorophenoxy)acetic acid, triadimenol, bitertanol and pentachlorophenol. Uptake was biphasic. A short (30-min) period with high rates of uptake was followed by uptake that proceeded more slowly and was steady over hours. Compartmentation of pesticides was studied by desorbing pentachlorophenol from leaves previously loaded with [¹⁴C]pentachlorophenol. From the uptake and desorption kinetics it was concluded that penetration of pesticides proceeds as follows: the compounds are first sorbed at the surface of epicuticular wax aggregates where they are in contact with the donor solutions. Solutes then diffuse through the surface wax aggregates into the cuticle. Equilibrium between donor solutions, surface wax and cuticle is established in about 30 min. After this time the amounts of solutes in these compartments no longer increase. Uptake after this time represents penetration into the leaf cells. This fraction of the pentachlorophenol is retained irreversibly, while that sorbed in wax and cutin can be desorbed again. All compounds were sorbed in cuticular waxes and partition coefficients wax/water were determined. On a mass basis only 5 to 10% of the amounts sorbed in cutin are sorbed in wax. This comparatively low solubility in wax contributes to the barrier properties of cuticular waxes. The other determinant of permeability is the very low mobility of solutes in cuticular waxes.     

Mobilities of organic compounds in reconstituted cuticular wax of barley leaves: Determination of diffusion coefficients

Isolated cuticular wax, obtained from barley leaves, was mixed with ¹⁴Clabelled organic chemicals including aromatic pesticides and long-chain linear alkanes, alcohols and acids. These mixtures were reconstituted from the melt and labelled chemicals were desorbed from the wax by immersing the wax samples in aqueous phospholipid suspensions. Diffusion coefficients (D) of radiolabelled test compounds in the wax were derived from desorption kinetics. Diffusion coefficients ranged from 10^?17 to 10^?22 m² s^?1 and decreased rapidly with increasing molar volumes of solutes. However, size selectivity of D was much more pronounced with the linear, long-chain molecules than with the aromatic compounds. It is argued that the two different groups of chemicals (compounds occurring naturally in cuticular waxes vs pesticide molecules) were trapped in different fractions of wax during crystallization from the melt. The normal long-chain aliphatic compounds appear to be incorporated into the crystalline fraction of the wax, while the cyclic pesticide molecules are confined to the solid amorphous regions. Our data indicate that constituents of cuticular waxes are not immobile. In fact, relatively small linear aliphatic molecules have mobilities that do not differ too much from those of cyclic pesticides. However, the pronounced size selectivity of diffusivities of long-chain aliphatic compounds causes a rapid decrease in D with increasing chain length. The value of D of hexadecanoic acid was 3.81 × 10^?18 m² s^?1 while that of dotriacontane was only 4.07 × 10^?22 m² s^?1. Thus, increasing the carbon number by a factor of two resulted in a decrease in mobility by almost four orders of magnitude. Diffusivities of selected pesticide molecules in reconstituted wax were compared with permeances measured using intact barley leaves and were found to be in satisfactory agreement.     

The hydrolysis of herbicidal phenoxyalkanoic esters to phenoxyalkanoic acids in Saskatchewan soils

The hydrolysis of the iso-propyl, n-butyl-and iso-octyl esters of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), the n-bytyl ester of 2,4-dichlorophenoxybutyric acid (2,4-DB) and the iso-octyl ester of 2,4-dichlorophenoxypropionic acid (2,4-DP) was studied in four prairie soils of differing textures and pH at 25±1°C. The esters were analysed using gas chromatography. After 24 h in soils at wilting point moisture, and above, less than 20% of the applied iso-propyl and n-butyl esters could be recovered from one soil type and none from the remaining three. Loss of the iso-cotyl esters was slower; however, no trace of the 2,4,5-T and 2,4-DP esters was observed in any of the moist soils after 48 and 72 h respectively. In all cases loss of all esters from air-dried soils minimal. The phenoxyalkanoic acid hydrolysis products were recovered from all soil types, treated with the various esters and identified using thin-layer chromatography.     

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

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

Effects of surfactants on water permeability of isolated plant cuticles and on the composition of their cuticular waxes

Treating the outer surfaces of isolated cuticles of Seville orange (Citrus aurantium L.) and pear (Pyrus communis L. cv. Bartlett) leaves with a number of nonionic (polyoxyethylene) surfactants increased their permeability to water by factors ranging from 4.1 to 14.7 and from 7.2 to 152.4, respectively. However, sodium dodecylsulphate, an anionic surfactant, had little effect on water permeability. In both species the major aliphatic constituents were n-alkanes, 1-alkanols and n-alkyl esters. None of the surfactant treatments altered the amounts or composition of waxes in the cuticles used for transport measurements. The reasons for the apparent absence of solubilization or dissolution of cuticular waxes by nonionic surfactants are discussed and a hypothesis is presented for the mechanism by which activator adjuvants may increase the permeability of plant cuticles.     

THE ABSORPTION,TRANSLOCATION AND METABOLISM CHARACTERISTICS OF 4-(2,4-DICHLOROPHENOXY)BUTYRIC ACID IN BIGLEAF MAPLE*

Summary. Detached leaves treated with 2,4-DB were used to demonstrate that the foliage of Acer macrophyllum Pursh. possesses the enzyme systems necessary for oxidation of the 2,4-DB side chain. Absorption and translocation studies showed that 2,4-DB was absorbed less but translocated more than some other phenoxy herbicides which have been tested on this species. Studies with excised stem phloem and excised roots showed that different plant tissues are not equally capable of decarboxylating 2,4-DB. An experiment with intact plants established that 2,4-DB was translocated unchanged, and that the primary product of the oxidation of 2,4-DB is 2,4-D. The results are discussed with respect to the translocation characteristics of this herbicide in bigleaf maple. Caractères de l'absorption, de la migration et du métabolisme de l'acide 4-(2,4-dichlorophénoxy) butyrique dans l'érable a grandes feuilles     

Leaf surface characteristics of apple seedlings, bean seedlings and kohlrabi plants and their impact on the retention and rainfastness of mancozeb

A study was made of the influence of the upper leaf surface characteristics on the retention and rainfastness of the contact fungicide mancozeb with and without tank-mix adjuvants (RSO 5 and RSO 60) on apple seedlings, bean seedlings and kohlrabi plants. Large differences in roughness, in the amount and composition of surface waxes and in the retention and rainfastness of mancozeb were found among species. Strong correlations between roughness and total amount of surface waxes and mass of C29 alkane in the wax mass were also found. Fungicide retention was strongly, negatively correlated with surface roughness, total epicuticular wax, amount of C29 alkane and the total mass of alkanes. Rainfastness correlated strongly or very strongly with the amount of C28 alcohol and C33 alkane. The addition of a more hydrophobic (RSO 5) or a more hydrophilic (RSO 60) adjuvant to the spray solution influenced retention and rainfastness, and also altered the correlation coefficients. The present results support earlier observations which show that the success of adjuvants in enhancing the retention and rainfastness of agrochemicals depends on the characteristics of the leaf surface.     

Epicuticular Wax and White Pine Blister Rust Resistance in Resistant and Susceptible Selections of Eastern White Pine (Pinus strobus)

ABSTRACT Epicuticular wax on needles was evaluated for its influence on Cronartium ribicola infection of resistant and susceptible selections of Pinus strobus. Environmental scanning electron microscopy comparisons revealed that needles from a resistant selection of eastern white pine, P327, had a significantly higher percentage of stomata that were occluded with wax, fewer basidiospores germinating at 48 h after inoculation, and fewer germ tubes penetrating stomata than needles from a susceptible selection H111. In addition, needles from seedlings that failed to develop symptoms 6 weeks after inoculation, from a cross between P327 and susceptible parent H109, had a significantly higher percentage of stomata occluded with wax compared with needles from seedlings that developed symptoms. In experiments where epicuticular waxes were removed from needles before seedlings were infected, resistant seedlings without wax developed approximately the same number of infection spots (as measured by spot index) as susceptible seedlings with wax intact. Gas chromatography/mass spectrometry comparisons of extracted epicuticular waxes revealed several peaks that were specific to P327 and not found in susceptible H111 suggesting biochemical differences in wax composition. These results implicate the role of epicuticular waxes as a resistance mechanism in P. strobus selection P327 and suggest a role for waxes in reducing spore germination and subsequent infection through stomatal openings.     

Control of Cirsium arvense (L) Scop, by herbicides and mowing

The efficacy of mowing and of herbicides (applied by spot spraying or boom spraying) for the selective control of Cirsium arvense (L) Scop, in Victorian pastures was investigated. The pastures were based on Trifolium repens L. and Lolium perenne L. A general decline in the number of thistle shoots in untreated plots at three out of five sites was recorded.‘Tordon 50-d' (5% a.i. picloram and 20% a.i. 2,4-D as triisopropanolamine salts), MCPB, 2,4-DB and mowing resulted in suppression, but not eradication, during the experimental period. MCPB and 2,4-DB are the most suitable herbicides for selective control. The use of‘Tordon 50-d' is restricted by its effect on clovers, soil persistence and cost. Variable growth of C. arvense, associated with variable summer rainfall in Victoria, increases the difficulty in controlling this weed and necessitates a persistent long term approach.     

Ethoxylated rapeseed oil derivatives as novel adjuvants for herbicides

Ethoxylates of rapeseed oil and of methylated rapeseed oil were synthesized and tested as adjuvants for 2,4-D and phenmedipham. Provided they had less than 6 units of ethylene oxide (EO), 1.0 to 10 g litre(-1) ethoxylates in water induced droplet spreading on barley leaves. In an acetone-based medium all derivatives strongly promoted the foliar uptake of 2,4-D, with no clear influence of the ethoxylation degree. In the same medium there was a negative influence of ethoxylate chain length on the foliar uptake of phenmedipham. In a water-based medium, phenmedipham applied with rapeseed oil emulsified with ethoxylated (20 EO) rapeseed oil displayed uptake rates close to a commercial preparation. The same was true for phenmedipham applied with ethoxylated (2 EO) methylated rapeseed oil. In bioassays, phenmedipham prepared with methylated rapeseed oil emulsified with ethoxylated (20 EO) rapeseed oil was as efficacious on barley as a commercial formulation. The same was true for phenmedipham prepared with ethoxylated (2 EO) methylated rapeseed oil. However, neither rapeseed oil nor methylated rapeseed oil emulsified with ethoxylated (2 EO) methylated rapeseed oil conferred good efficacy to phenmedipham. Hence, ethoxylated rapeseed oil derivatives are promising adjuvants or formulants for herbicides.     

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.     

Normal germling development by Erysiphe graminis on cereal leaves freed of epicuticular wax

Experiments were conducted to test the hypothesis that recognition of the physical structure of epicuticular leaf waxes by Erysiphe graminis may be important to the development of normal germlings and the formation of functional appressoria. Comparisons of germination rates and characteristics of germling development by E. graminis f.sp. avenae , and in one experiment by f.sp. hordei , were made between intact cereal leaves and leaves from which the epicuticular waxes had been stripped away.
Overall, fungal development was very similar on intact and wax-free leaves: although germination rates were slightly, but significantly, lower, and lengths of appressorial germ tubes slightly greater, on stripped than intact leaves, a very similar proportion of germlings formed apparently normal appressoria in both cases. This was true for f.sp. avenae on first- and fifth-formed leaves of susceptible and adult plant resistant oats, and on barley and wheat first leaves, and for f.sp. hordei on first leaves of barley, oat and wheat. The appressoria formed on stripped leaves not only appeared normal, but also formed haustoria with at least the same frequency as on intact leaves; in several experiments, a higher proportion formed haustoria in stripped than intact leaves. Wax removal did not affect the adult plant resistance of oat cv. Maldwyn, which limits haustorium formation by appressoria, indicating that epicuticular wax was not involved in this resistance. It is concluded that the physical structure of epicuticular wax is not involved in the recognition processes leading to normal germling development.     

Relative persistence of di-and tri-chlorophenoxyalkanoic acid herbicides in Saskatchewan soils

The persistence of 2,4-D, 2,4-DB, dichlorprop, 2,4,5-T, and fenoprop at the 2 ppm level was studied in the laboratory on three prairie soils at 85% of field capacity and 20°C. Following extraction of the soils with aqueous acetonitrile containing acetic acid, the herbicidal acids remaining were analysed gas chromatographically. Breakdown was rapid on all soils and the average half-lives for 2,4-D, 2,4-DB, dichloroprop, 2,4,5-T, and fenoprop were < 7, < 7, 10, 12, and 12 days respectively. Degradation on air-dried soils (15% of field capacity) was negligible with over 85% of the applied herbicides being recoverable after incubation periods during which the herbicides remaining in the moist soils accounted for less than 30% of the original treatments. Persistance relative des acides di et tri-chlorophénoxy-alkanoï-ques herbicides dans des sols du Saskatchewan. La persistance du 2,4-D, du 2,4-DB, du dichlorprop, du 2,4,5-T et du fénoprop, à la concentration de 2 ppm, a étéétudiée au laboratorire, sur trois sols de prairie, a 85% de la capacité au champ et a 20°C. Après leur extraction des sols par l'acétonitrile aqueux contenant de l'acide acétique, les acides herbicides restants ont été analysés par chromatographie en phase gaseuse. La dégradation a été rapide pour tous les sols et les demi-vies moyennes du 2,4-D, du 2,4-DB, du dichlorprop, du 2,4,5-T, et du fénoprop ont été respectivement de <7, <7, 10, 12 et 12 jours. La dégradation sur des sols séchés a l'air (15% de la capacité au champ), a été négligeable, plus de 85% des quantités d'herbicides appliquées étant récupérables après des périodes d'incubation durant lesquelles les herbicides restant dans les sols humides ne représentaient plus que moins de 30% des quantités apportées à l'origine. Relative Persistenz von Di-und Trichlorphenoxyalkansäure-Her-biziden in Böden Saskatchewan In Laborversuchen wurde die Persistenz von 2,4-D, 2,4-DB, Dichlorprop, 2,4,5-T und Fenoprop in drei Prärieböden festgestellt. Die Versuche wurden bei 20°C, 85 % der Feldkapazität und einem anfänglichen Herbizidgehalt der Böden von 2 ppm durchgeführt. Die Extraktion der Böden erfolgte mit wässerigem Acetonitril mit einem geringen Anteil an Essigsäure. Die Herbizide wurden gaschromatographisch nachgewiesen. In allen Böden wurde ein schneller Abbau festgestellt. Die Halbwertszeiten betrugen für 2,4-D, 2,4-DB, Dichlorprop, 2,4,5-T und Fenoprop < 7, < 7,10, 12 bzw. 12Tage. Der Abbau im lufttrockenen Boden (15% der Feldkapazität) war zu vernachlässigen. Hier waren noch mehr als 85% der ausgebrachten Herbizidmenge vorhanden, wenn in den feuchten Böden die Konzentration bereits weniger als 30% betrug.     

Investigations on the role of cuticular wax in resistance to powdery mildew in grapevine

Cuticular wax on the plant epidermis inhibits or enhances prepenetration events of powdery mildew (Erysiphe necator Schwein). We examined the role of cuticular leaf and berry waxes as a resistance mechanism in four grapevine genotypes (Italia?×?Mercan-174, Gürcü, Isabella, Özer Karas?) resistant to powdery mildew after natural infection and inoculation. To understand cuticular wax properties, we determined the amount of wax and antifungal effects of thin layer chromatography (TLC) fractions from cuticular leaf and berry waxes, then assessed the chemical composition of fractions with different antifungal activities using gas chromatography/mass spectrometry (GC/MS). Susceptible genotypes Cabernet Sauvignon and Italia were used for comparison. Resistant and sensitive genotypes did not differ significantly in the total amount of wax on leaves and berries; however, 27 fatty acids, 26 alkanes, 6 terpenes, 4 indole derivatives and 4 ketones, and 3 amides, 3 phenols and 3 steroids were detected in fractions with high antifungal activity (≥75% inhibition of germination) in leaf and/or berry cuticular waxes of resistant genotypes only. These compounds may be evaluated as markers for powdery mildew resistance during genotype selection in a grapevine breeding program.     

Influence of cuticular waxes on penetration of pear leaf cuticle by 1-naphthaleneacetic acid

Removal of waxes from the upper pear leaf cuticle by chloroform extraction greatly increased sorption of naphthaleneacetic acid (NAA) into the cuticle. Penetration of NAA through isolated upper pear leaf cuticle was likewise increased following wax removal by chloroform extraction. Plating pear leaf wax back onto dewaxed cuticle surfaces reduced sorption and penetration.     

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     

Mechanisms of cuticular uptake of xenobiotics into living plants: 1. Influence of xenobiotic dose on the uptake of three model compounds applied in the absence and presence of surfactants into Chenopodium album, Hedera helix and Stephanotis floribunda leaves

This study determined the uptake of three model compounds, applied in the presence and absence of surfactants, into the leaves of three plant species (Chenopodium album L, Hedera helix L and Stephanotis floribunda Brongn). The results with 2-deoxy-D-glucose, 2,4-dichlorophenoxyacetic acid and epoxiconazole in the presence ofsurfactants (the polyethylene glycol monododecyl ethers C12EO3, C12EO6, C12EO10 and a trisiloxane ethoxylate with mean EO of 7.5, all used at one equimolar concentration and therefore different percentage concentrations) illustrate 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 xenobiotics studied over a wide concentration range in the presence of these surfactants. Uptake on a unit area basis (nmol mm(-2)) could be related to the initial dose of xenobiotic applied per unit area (ID) by an equation of the form: Uptake = a [ID]b at time t = 24h. ID is given by the mass of xenobiotic applied, M divided by the droplet spread area, A. Total mass uptake is then calculated from an equation of the form: Total Uptake = a [ID]b x A.     

Effect of adjuvants on the performance of the new cereal fungicide,metconazole. I glasshouse trials

Metconazole, (1RS, 5RS; 1RS, 5SR)-5-(4-chlorobenzyl)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, is a highly active fungicide, in particular controlling seed-borne and foliar diseases of cereals, such as wheat (Triticum aestivum L.) and barley (Hordeum vulgare L.). In order to maximize its foliar activity, an experimental survey of some types of surfactants and an emulsifiable oil was undertaken. Two types of metconazole formulation were investigated using a biological assay involving the therapeutic control of two diseases (Erysiphe graminis DC f. sp. tritici Marchal and Leptosphaeria nodorum Muell.) of wheat. Enhancements of activity by ?Genapol’? C12/C14 alcohol ethoxylates of an emulsifiable concentrate (ECM) formulation of metconazole were approximately three- to four-fold. For its, initially, less active suspension concentrate (SCM) formulation, enhancements were around 35-fold, so that with these adjuvants the two formulations were of similar activity. The enhancement ability of these ?Genapol’? surfactants was optimal at lower (5–10 moles) ethylene oxide content. These analogues induced marginally better enhancements of activity than members of a range of nonylphenol ethoxylates (?Arkopal’?), and emulsifiable paraffinic/naphthenic oil (HVI 60E) and a castor oil ethoxylate (?Atlas’? G1281) but were equivalent to a similar series of alcohol ethoxylates (?Dobanol’?) from another source. Varying the alkyl chain length between C₉-C₁₁ and C₁₄-C₁₅ in the ?Dobanol’? series had little effect on their high enhancements of metconazole activity. It was determined from trials varying the application rate of the best alcohol ethoxylates that application rates of 1–1.5 kg ha^?1 were required for maximum activity. This implied the use of high adjuvant/metconazole ratios in one-pack adjuvant-containing formulations. A range of soluble liquid (SL) formulations were prepared with either ?Dobanol’? 23–6.5 or ?Dobanol’? 91-6/metconazole ratios varying from 5:1 to 15:1. There were found to be highly active and were recommended for field testing.