Effects of nonionic surfactants on cuticular sorption and penetration of 2, 4-dichlorophenoxy acetic acid

Surfactants increase the uptake of some foliar-applied chemicals to a greater extent than would be expected from their effects on surface tension and spray coverage. This study of the uptake of 2, 4-D [(2, 4-dichlorophenoxy)acetic acid] evaluated the effect of surfactants on penetration through and sorption by isolated cuticles of apple leaves. [¹⁴C]2, 4-D was placed in glass chambers affixed to enzymatically isolated adaxial apple leaf cuticles after the cuticle segments had been treated with various surfactants. The same surfactant pretreatments were included in sorption studies in which cuticle segments were immersed in [¹⁴C]2, 4-D for 96 h. Quantities of 2, 4-D passing through or sorbed by the cuticle were determined. Similar experiments were conducted with unaltered cuticles and cuticles dewaxed with chloroform. The hydrophile-lipophile balance (HLB) of polyethylene-glycol-based surfactants was inversely related to the sorption of those surfactants by the cuticles and penetration of 2, 4-D. Sorption of 2, 4-D by apple leaf cuticles was unaffected by surfactant pretreatment. Dewaxed cuticle membranes showed a similar response to 2, 4-D penetration and sorption following the surfactant pretreatment.     

Cuticular sorption and desorption of a nonionic diethylene glycol monooleate surfactant

Sorption and desorption of ‘Pegosperse’ 100-O(PEG 100-O; diethylene glycol monooleate, containing 15% diester) surfactant by unaltered (CM) and dewaxed (DCM) adaxial cuticle membranes isolated from apple (Malus pumila M.) leaves were studied. The aim of this study was to understand interactions between surfactants and cuticles. Enzymatically isolated cuticles were soaked in buffer or PEG 100-O solution (pH 7–0). and the weight changes of cuticles were measured to determine the amount of surfactant sorbed or desorbed by the cuticles. For very low surfactant concentrations, sorption was measured by changes in the surface tension of the solutions. PEG 100-O sorption by both the CMs and the DCMs occurred mainly in the first three hours and was concentration-dependent. The DCMs always sorbed more surfactant than the CMs. Desorption of PEG 100-O from both CMs and DCMs was rapid in the first few hours and then decreased to a relatively low rate until the surfactant was totally desorbed from the cuticles after about two months. The sorption and complete desorption of the surfactant by both CMs and DCMs show that PEG 100-O interacts with both cutins and waxes of the cuticles and the interactions are reversible.     

Finite dose diffusion studies: I. Characterizing cuticular penetration in a model system using NAA and isolated tomato fruit cuticles

A finite dose diffusion system was employed to study cuticular penetration of 2‐(1‐naphthyl) [1−¹⁴C]acetic acid (NAA) from simulated spray droplets through enzymatically isolated tomato fruit cuticles (Lycopersicon esculentum Mill cv Pik Red). Isolated cuticles were mounted on diffusion half‐cells with the cell wall surfaces facing a 20 mM citric acid receiver solution (pH 3.2, volume 2.9 ml, prepared with deionized water). A 5‐µl donor droplet containing NAA at 100 µM in 20 mM citric acid buffer (pH 3.2) was applied to the outer surface. Penetration was monitored by repeated sampling of the receiver solution. NAA penetration was characterized by (1) an initial lag phase of about 2.3 h, (2) a phase of nearly constant maximum rate of penetration averaging 6.3% of applied NAA h⁻¹ (equivalent to 0.032 nmol h⁻¹) and (3) a plateau phase approaching an asymptote at 81.2% of applied NAA (equivalent to 0.406 nmol) at 120 h. Within 1 h after application droplets appeared dry on visual inspection. Immediately after droplet drying, 7.0% of the applied NAA was sorbed to the cuticle, but only 0.5% penetrated into the receiver solution, indicating that penetration occurred almost exclusively from the apparently dry deposit. At 120 h, 5.2% of the NAA applied was associated with the deposit and 4.3% with the cuticle. The distribution of maximum rates of penetration was log‐normal, but penetration at 120 h followed a normal distribution. Cuticle thickness (estimated 5–25 µm) had no significant effect on NAA penetration. Maximum rates of penetration through pepper fruit and citrus and ficus leaf cuticles were 4.9‐, 2.6‐ and 0.1‐times that through tomato fruit cuticles. At 120 h, penetration averaged 85.5, 79.5 and 34.7% for pepper, citrus and ficus cuticles, respectively. Extracting epicuticular and embedded waxes increased NAA penetration rates through tomato fruit cuticle more than three‐fold, but had little effect on penetration at 120 h (71.0 vs 87.7% for cuticular vs dewaxed cuticular membranes). The maximum penetration rate and total penetration were found to be useful parameters in describing the penetration time‐course. © 2000 Society of Chemical Industry     

Concentration-Dependent Mobility of Chlorfenvinphos in Isolated Plant Cuticles

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

Modelling penetration of plant cuticles by crop protection agents and effects of adjuvants on their rates of penetration

A theory of cuticular penetration of crop protection agents (CPAs) is presented, which incorporates properties of cuticles and cuticular waxes as well as properties of active ingredients and adjuvants. Based on this theory, two models are developed which are analytical in the sense that they help to quantify and understand (i) differences in permeability among cuticles from different species, (ii) effects of properties of CPAs on permeabilities of cuticles and rates of uptake and (iii) the effects of adjuvants on properties of cuticles and rates of uptake of CPAs. The models can be used to predict rates of uptake of CPAs as affected by properties of cuticular waxes, active ingredients and adjuvants. However, before this can be done, a constant, two parameters and at least two variables must be estimated. Properties of cuticles are accounted for by the constant D⁰/Δx and the parameter β′. The former, the ratio of the mobility of a hypothetical molecule having zero molar volume (D⁰x) divided by the path length (Δx) across the cuticle, has the dimension of velocity (ms^?1) and is independent of the solubility of the CPA. The latter is a measure of size selectivity of the cuticle. Differences in permeabilities of cuticles from different species increase with increasing size of active ingredients due to size selectivity (β′). Removing cuticular waxes from Citrus cuticles increased D⁰/Δx by a factor of 2042, while β was not affected. Differential solubility of CPAs is considered part of the driving force and at least two different partition coefficients are needed to account for differences in solubilities in cuticular waxes, cutin, water and the formulation residue on the surface of the cuticles. Adjuvants are solvents in the formulation residue on the leaf surface once the carriers (water and other volatile solvents) have evaporated and certain adjuvants also act as accelerators; they penetrate the cuticle and increase D⁰/Δx. Thus, accelerators increase rates of uptake and this effect depends on two factors, (i) the intrinsic activity of the accelerator and (ii) rate of penetration into the cuticle, because the active ingredients follow the accelerator front across the cuticle. Since accelerators penetrate from the formulation residue into the cuticle, the volume of the formulation residue decreases with time. This maintains high concentrations of CPAs in the formulation residue and, thus, maximum driving forces and rates of penetration. To utilise fully this dual accelerator effect, it is necessary to match velocities of penetration of accelerators and active ingredients accurately.     

Characterizing pesticide and surfactant penetration with isolated plant cuticles

A survey is presented of the use of isolated leaf and fruit cuticles in studying foliar penetration. Isolated cuticles, which represent the prime barrier to penetration, provide a physical system with which transport studies can be conducted under well-defined and highly controlled conditions while avoiding the physiological effects of biologically active compounds on the system. Most studies with isolated cuticles have focused on sorption, desorption and infinite-dose cuticular transport of compounds in aqueous systems. Partition coefficients can be calculated for pesticides from sorption data, thereby yielding information on the solubility of the compounds in the cuticle. Permeance and diffusion coefficients can be calculated from cuticular transport studies. These transport parameters provide for a better understanding of the mechanisms of cuticular penetration. Further, they are useful in comparing both the penetration characteristics of selected compounds and permeability of cuticles. Transport systems, using isolated cuticles, may be used to quantify the effects of spray additives on pesticide penetration. A finite-dose system is described that may be useful in studying spray droplet/deposit interactions with the cuticle and, concurrently, following transcuticular penetration from droplets/deposits on the surface. These systems may prove useful in optimizing spray formulations and spray parameters, leading to more efficient pesticide development and application.     

Penetration of clopyralid and related weak acid herbicides into and through isolated cuticular membranes of Euonymus fortunei

A model system consisting of chemically isolated cuticular membranes placed on agar was used to study the penetration of various formulations of ¹⁴C-labelled clopyralid, fluroxypyr, triclopyr, picloram, and 2,4-D into and through cuticular membranes. Clopyralid, commercially formulated as the acid, or 1-decyl ester was rapidly absorbed after 12 h by isolated cuticles of Euonymus fortunei. There was less absorption of the monoethanolamine and potassium salt formulations when compared to the acid and 1-decyl ester. However, in terms of the absorbed ¹⁴C-activity that partitioned into the agar, there was no difference between the acid and salt formulations with approximately 90% being partitioned after 48 h. Conversely, the 1-decyl ester formulation of clopyralid was retained in the cuticle; less than 5% of the absorbed fraction was recovered in the agar after 48 h. When the acid forms of clopyralid, fluroxypyr, triclopyr, picloram, and 2,4-D were compared, there was little or no difference in absorption among the herbicides. However, the ¹⁴C-activity from clopyralid partitioned the most (90%) and triclopyr the least (50%) into the agar. When ester formulations of clopyralid, fluroxypyr, and triclopyr were compared, at least 95% of the ¹⁴C-activity was absorbed 24 h after application. However, of the amount absorbed, significantly more of the butoxyethyl ester of triclopyr (36%) partitioned into the agar than did the 1-decyl ester of clopyralid (6%) or the 1-methylheptyl ester of fluroxypyr (5%). Differential retention of various herbicide formulations in this model system may explain, in part, the differences in absorption and translocation among radiolabelled clopyralid formulations observed in previous research (Kloppenburg & Hall, 1990).     

Effects of alcohols,glycols and monodisperse ethoxylated alcohols on mobility of 2,4-D in isolated plant cuticles

Effects of n-alcohols, ethoxylated alcohols and glycols on mobility of 2,4-dichlorophenoxy acetic acid (2,4-D) in cuticular membranes (CM) isolated from bitter orange (Citrus aurantium L.) leaves were studied. 1-Heptanol, 1-octanol and 1-nonanol had the highest effects, as they increased solute (2,4-D) mobility by 25- to 30-fold. Increasing the number of carbon atoms in the alcohols decreased their effectiveness. Ethoxylation of alcohols did not increase 2,4-D mobility and effectiveness decreased with increasing ethoxylation. Free glycols had no effect on solute mobility in isolated cuticles. The results show that ethoxylation is not required for increasing solute mobility in cuticles. It is suggested that alcohols and ethoxylated alcohols are sorbed in cuticular waxes and plasticize them. The data show that alcohols and ethoxylated alcohols having between seven and ten carbon atoms are powerful accelerator adjuvants, as long as the degree of ethoxylation is not too high. Free short-chain alcohols synthesized by leaves may act as endogenous plasticizers and modulate permeabilities of cuticles, depending on environmental and growing conditions.     

Herbicide penetration across isolated and intact leaf cuticles

Penetration of four herbicides (atrazine, diclofop-methyl, dinoseb and glyphosate-mono(isopropylammonium) salt) was followed through isolated pear leaf cuticles into agar and across intact cuticles of Argenteum (ARG) mutant pea leaves from monosized droplets (300 μ diam.) during 48 h following application. Penetration into pea leaves ranged from low for glyphosatemono(isopropylammonium) (5% of amount applied) and atrazine (14%) to rapid for dinoseb (91%) and diclofop-methyl (82%). A major proportion (90%) of the dinoseb retained in the tissues underlying the site of droplet application migrated across the cuticle and the epidermal layer of cells. In contrast, only a small proportion (13%) of the dinoseb entering the leaf was transported to the tissues surrounding the treatment zone. Corresponding values for diclofop-methyl were 61% and 4% respectively. Initially, dinoseb also penetrated rapidly through isolated pear leaf cuticles, 36% of the applied dose being recovered in an agar receiver disc 4 h after treatment, but subsequent uptake was slower. Penetration of glyphosate-mono(isopropylammonium) also decreased after 4 h whereas atrazine and diclofop-methyl diffused steadily through isolated cuticles up to 216 h after treatment. The incorporation of ‘Tween 20’ or ‘Agral 90’ (1 g litre^?1) into the formulation reduced the penetration of glyphosate-mono(isopropylammonium) through isolated pear leaf cuticles.     

Polydisperse ethoxylated fatty alcohol surfactants as accelerators of cuticular penetration. 2: Separation of effects on driving force and mobility and reversibility of surfactant action

Polydisperse ethoxylated fatty alcohol (EFA) surfactants can improve the performance of crop protection agents. At the cuticular level they act as accelerators of penetration by increasing the mobility of active ingredients in the cuticle, the barrier properties of which are mainly caused by cuticular waxes. Polydisperse Genapol C-050 (GP C-050, average formula C12.5E5.8) was also found to increase mobility in wax-extracted polymer matrix membranes (MX) of bitter orange and pear, indicating that sorption of surfactants increased segmental mobility of polymethylene chains in cutin and wax. Sorption into MX of the active fraction of GP C-050 from 5g litre⁻¹ micellar solutions was in equilibrium in less than 1 h after establishing contact. This is almost 100-fold faster than with cuticular membranes (CM). Temperature dependence of solute mobilities in CM was studied in order to measure activation energies (E_D) of diffusion in the presence and absence of aqueous surfactant solutions. Monodisperse fatty alcohol ethoxylates C8E3, C8E4 and C12E6, and (non-surface-active) tributylphosphate decreased E_D of the model compounds WL 110547 and bifenox in Citrus, Pyrus and Stephanotis CM by more than 100 kJ mol⁻¹. This corresponds to 50 to 275-fold increases of mobilities at 15 °C. Our data suggest that the decrease in activation energies with the concomitant accelerating effect on mobility contributes considerably to the effects of so-called activator surfactants. High temperature and accelerators act similarly on barrier properties of CM. It is shown that effects of both monodisperse and polydisperse EFA surfactants on solute mobility are reversible and that radiolabelled C12E8 penetrated pear CM rapidly. However, rates of penetration were lowered by excess amounts of WL 110547 and especially phenylurea. Partition coefficients of seven organic solutes between Capsicum fruit cuticles and GP C-050 were very low and, with the exception of methylglucose, smaller than 1. They decreased with lipophilicity and differed about 100-fold. Especially for the lipophilic compounds they were orders of magnitude lower than octanol/water or cuticle/water partition coefficients, which indicates the limited usefulness of these values for an understanding of penetration of active ingredients from formulation residues. © 1999 Society of Chemical Industry     

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.     

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.     

Growth behaviour and leaf morphology of Philippine strains of Sphenoclea zeylanica showing differential response to 2,4-D

The germination and growth of three strains of gooseweed (Sphenoclea zeylanica Gaertn.) that showed susceptibility, moderate susceptibility, and tolerance for foliar-applied 2,4-D isobutyl ester were studied in the laboratory and greenhouse. The plants were isolated from samples collected from major rice (Oryza sativa L.) growing areas in the Philippines. The seeds of all three strains possessed dormancy; light stimulated germination but did not completely overcome dormancy. Without N application, stem elongation and leaf production did not differ among the strains. With 60 kg N ha^?1, the susceptible and moderately susceptible strains responded better than the tolerant strain, the difference being apparent at 6 weeks after emergence. Measurements of the leaf cuticle showed significant differences among the strains starting at the 8- to the 10-leaf stage, a trend that paralleled their response to 2,4-D. Adding a surfactant to the spray formulation nullified the differential responses. Implications for managing the weed and correlations with current field observations are discussed.     

Recent developments in our understanding of the plant cuticle as a barrier to the foliar uptake of pesticides†

The plant cuticle is a highly complex membrane which forms the outer surface of the aerial portion of plants. The nature of the plant cuticle is reviewed with particular regard to its action as a potential barrier to the penetration of pesticide molecules; the role of the cuticular waxes is highlighted. The physicochemical properties of the cuticle influence the behaviour of spray droplets and, in turn, may affect the rate and efficiency of cuticle penetration. The permeation of active ingredients is influenced by their solubility characteristics as indicated by octanol/water (log K_ow) and cuticle/water (K_cw) partition coefficients. Penetration of hydrophilic compounds (low log K_ow) may be enhanced by hydration of the cuticle, while transcuticular transport of non-polar solutes (high log K_ow) is increased by factors which reduce wax viscosity. The use of in-vitro models involving isolated cuticle membranes, isolated cuticle waxes, or isolated leaves has helped to focus on the activities of the cuticle in the absence of other physiological factors. Using these systems, the role of the waxes as a transport-limiting barrier has been identified and the factors influencing sorption, permeance and desorption examined. The action of surfactants, in vitro and in vivo, has been briefly addressed in regard to their role in facilitating cuticle penetration; other steps involving surfactant/solute/cuticle are complex, and synergy appears to depend on a number of factors including test species, concentration of active ingredient, surfactant type and concentration. Adjuvants may greatly influence the surface properties of the droplet, predispose the cuticle to solute transport, and enhance pesticide activity. The nature of these complex inter-relationships is discussed. © 1999 Society of Chemical Industry     

Antagonistic effects of 2,4-D amine and bentazone on control of Avena fatua with tralkoxydim

Control of Avena fatua with tralkoxydim was significantly reduced in glasshouse experiments when the herbicide was tank-mixed with either 2,4-D amine or bentazone. Antagonism increased with increasing rates of these broadleaf herbicides in the tank-mixture and it could, in turn, be decreased by increasing rates of tralkoxydim. When herbicide solutions were applied to single leaves with a micropipette applicator, bentazone was antagonistic only when mixed in the same droplet with tralkoxydim and not when the two herbicides were applied adjacently in separate droplets. In contrast, both separate and combined applications of 2,4-D amine and tralkoxydim were antagonistic. There was no antagonism when mixtures with either 2,4-D amine or bentazone were applied between the leaf sheath and culm. Antagonism could be circumvented by sequential applications of the herbicides. When tral-oxydim was applied first, there was no loss of A. fatua control if bentazone application was delayed 0.5 h or if 2,4-D amine was delayed 24 h. Results suggest that bentazone affects only cuticular penetration of tralkoxydim, whereas 2,4-D amine also influences subsequent translocation.     

Penetration of triolein and methyl oleate through isolated plant cuticles and their effect on penetration of [14C]quizalofop-ethyl and [14C]fenoxaprop-ethyl

The penetration of two model seed oil compounds, [¹⁴C]triolein (TRI) and [¹⁴C]methyl oleate (MEO) through plant cuticles and their effects on the penetration of [¹⁴C]quizalofop-ethyl and [¹⁴C]fenoxaprop-ethyl were investigated. Experiments were carried out using isolated cuticles from rubber plant (Ficus elastica Roxb.) leaves and from tomato (Lycopersicon esculentum Mill,) and pepper (Capsicum annuum L.) fruits. Chemicals were deposited in droplets on to cuticle discs maintained on agar blocks under controlled conditions. TRI and MEO were used at 1% (V/V). The transfer of radiolabel through cuticles was negligible for TRI and varied from 6 to 13% after 72 h, according to species, for MEO, The penetration results obtained for quizalofop-ethyl (0.084 mg mL^-1) and fenoxaprop-ethyl (0.189 mg mL^-1) were very similar and varied according to species. The greatest diffusion intoagar was observed for pepper (12.8% and 10.7% after 72 h, for quizalofop-ethyl and fenoxaprop-ethyl respectively), the lowest for rubber plant cuticles (1.4 and 1.3% respectively). Addition of MEO produced significant increases in the penetration of quizalofop-ethyl and fenoxaprop-ethyl through rubber plant and tomato cuticles. TRI had an enhancing effect on the two herbicides only with rubber plant cuticles. Results are discussed with particular consideration of the variations between plant species and the possible mode of action of seed oil adjuvants.     

Inhibition of chitin synthesis by benzoyl-phenylurea insecticides,III. Similarity in action in Pieris brassicae (L.) with Polyoxin D

The increase in cuticle thickness with age of fifth instar larvae of Pieris brassicae (L.) was measured microscopically. The injection of a lethal dose of either Polyoxin D or diflubenzuron revealed total inhibition of cuticular growth and caused comparable abnormalities in the cuticles.In a further experiment [¹⁴C]glucose was injected along with Polyoxin D into Pieris brassicae and the incorporation of radioactivity into various tissue fractions was measured. This revealed that the impairment of cuticular growth was due to inhibition of chitin synthesis.With the methods used the effects of Polyoxin D and two benzoylphenylurea insecticides appeared to be the same.     

Spray application factors and plant growth regulator performance: II. Foliar uptake of gibberellic acid and 2,4-D

Effects of droplet size and carrier volume on foliar uptake and translocation of gibberellic acid (GA₃) and 2,4-D were investigated. Simulated spray droplets were applied to primary leaves of 10-day-old Phaseolus vulgaris (cv Nerina) in droplet sizes and carrier volumes ranging from 0.5 to 10 μl and 10 to 200 μl per leaf, respectively. Doses of GA₃ (2 μg per leaf) and 2,4-D (100 μg per leaf) were held constant. Total uptake of GA₃ approached a penetration equilibrium within 24 h after application, but uptake of 2,4-D continued to increase. Decreasing droplet size and/or increasing carrier volume increased GA₃ and 2,4-D uptake. Translocation to stem and roots was positively related to total uptake. A positive linear relationship between the logarithm of the total droplet/leaf surface interface area and 2,4-D uptake or translocation was found, but for GA₃ this relationship was quadratic. Potential mechanisms of the effects of spray application factors on foliar uptake are discussed. © 1999 Society of Chemical Industry     

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.     

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.