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     

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.     

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.     

Decreased nerve sensitivity and decreased cuticular penetration as mechanisms of resistance to pyrethroids in a (1R)-trans-permethrin-selected strain of the house fly

A fenthion-resistant strain of the house fly (Musca domestica L.) was selected with bioresmethrin resulting in ca. 90-fold resistance to the selecting agent. This strain was subsequently selected with (1R)-trans-permethrin producing ca. 140-fold resistance to this latter insecticide. The permethrin-resistant (147-R) strain was highly cross-resistant to several other pyrethroids and demonstrated resistance to knockdown by these insecticides as well as by DDT. The sensitivity of the central nervous system to four pyrethroids was investigated. The 147-R strain was 2.6-fold less sensitive to (1R)-trans-ethanoresmethrin than the susceptible (NAIDM-S) strain, and >43-fold and >67-fold less sensitive to (1R,S)-cis, trans-tetramethrin and (1R)-trans-permethrin, respectively. It also displayed decreased penetration of (1R,S)-trans-[¹⁴C]permethrin when compared to the NAIDM-S strain. Lower nerve sensitivity and decreased cuticular penetration are potential mechanisms of resistance to pyrethroids in house flies in the United States.     

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     

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.     

Germination of chlamydospores of Fusarium oxysporum f. sp. pisi race 1 in the rhizosphere,and penetration of the pathogen into roots of a susceptible and a resistant pea cultivar

Germination of chlamydospores ofFusarium oxysporum f. sp.pisi race 1 in the rhizosphere of pea seedlings and red clover seedlings grown in natural soil heavily infested with the pathogen, was highest in percentage along the actively growing parts of the roots. At these sites, exudation of ninhydrinpositive substances and reducing sugars was most intense with seedlings grown in vitro.No significant difference in the percentage of germinating chlamydospores ofFusarium oxysporum f. sp.pisi race 1 were observed in the rhizosphere soil and on the root surface of homologous parts of roots of seedlings and mature plants of a susceptible Rondo and a resistant Rovar pea cultivar grown in natural soil heavily infested with the pathogen. Differences in the growth of mycelium of the pathogen on the root surface, or in the attachment of the mycelium to the root surface of both cultivars were not observed. Epidermis and cortex cells of roots of both cultivars reacted on penetration by the pathogen by producing a cellulose thickening of the cell wall, which later became infiltrated with a ligning-like material. A selective effect on the activities of the pathogen in the rhizosphere, on the root surface and in the epidermis and cortex in relation to resistance thus could not be demonstrated. Formation of new chlamydospores from germ tubes of germinating chlamydospores was frequently observed in the rhizosphere of the susceptible and resistant pea cultivar and in the rhizosphere of red clover seedlings.     

Effects of soil and crop management practices and pedo‐hydrological conditions on the seedbank size of Galinsoga spp. in organic vegetable fields

Galinsoga quadriradiata and Galinsoga parviflora are very troublesome weeds in many organic vegetable crops in Europe. A very straightforward method to keep Galinsoga infestations under control is by targeting the Galinsoga seedbank. To identify cropping systems able to reduce the seedbank size in vegetable‐based cropping systems, the relationships between the seedbank size of Galinsoga species and prevailing soil/crop management practices and pedo‐hydrological conditions were investigated. Hereto, the seedbank of the 0–20 cm topsoil layer was sampled in 50 organic vegetable fields and analysed according to the seedling emergence method. Field history data were collected for the past 5 years, and physical, chemical and microbial soil quality was determined. Galinsoga quadriradiata was the most frequent and abundant Galinsoga species in the weed seedbank. The genus Galinsoga was present in 90% of the soil weed seedbanks of organic vegetable fields but displayed wide variation in abundance. Smallest Galinsoga seedbanks were found in fields that were predominantly tilled with non‐inversion implements or rotationally ploughed, and continuously cropped with competitive crops during the entire growing season (April 15‐November 15). Contrary to G. quadriradiata, seedbank size of G. parviflora was closely related to soil organic carbon content and sand fraction. Remarkably, soils with a low level of easily plant‐available phosphorus and concomitant high activity of arbuscular mycorrhizae had smaller G. quadriradiata seedbanks. To reduce Galinsoga infestations, fields should preferably be tilled without soil inversion, fertilised with organic amendments with low content of readily plant‐available phosphorus and cropped with competitive crops all season long.     

Simulation of damage in winter wheat caused by the grain aphid Sitobion avenae. 1. Quantification of the effects of honeydew on gas exchange of leaves and aphid populations of different size on crop growth

Damage in winter wheat caused by the grain aphidSitobion avenae F., was studied in the laboratory and at field level.Honeydew substitute solution was applied to flag leaves of winter wheat plants. One and fifteen days after application, the rates of net carbon dioxide assimilation and transpiration were measured. The rate of dark respiration was significantly higher one day after application of honeydew substitute as compared to the control. Other parameters describing the carbon dioxide — light response were not significantly affected. Fifteen days after honeydew substitute application, the two experimental years yielded different results. Under hot and dry conditions, the rate of dark respiration was higher while the late of carbon dioxide assimilation at high irradiance, the mesophyll conductance and the leaf nitrogen content were lower than for the untreated control. In addition, chlorotic symptoms were visible. At moderate temperature and relative humidity, the initial light use efficiency was significantly lower fifteen days after treatment with honeydew substitute whereas other parameters were not significantly affected.In field experiments at two locations natural aphid populations consisting of mainlyS. avenae were treated weekly with an aphicide from crop development stages DC 71, 73, 75 and 77, respectively, to create infestations of different size and duration. In the unsprayed controls densities reached 15.8 and 44.4 aphids per tiller, amounting to 182 and 544 aphid-days, respectively. Crop samples were analysed weekly, starting at flowering. At the smaller natural infestation, no significant effect on any yield component nor on yield was found at any treatment. The larger infestation caused a significant reduction of leaf area index, leaf weight, amount of water-soluble carbohydrates and grain weight on various sample dates when the infestation was not sprayed before DC 75. No effects were found on tiller and grain density nor on nitrogen content of plant parts at harvest.Samenvatting Schade in wintertarwe veroorzaakt door de grote graanluisSitobion avenae F., werd bestudeerd in laboratarium-en veldproeven.De vlagbladeren van wintertarweplanten werden behandeld met honingdauw-substituut-oplossing. Eén en vijftien dagen na behandeling werden de netto fotosynthesesnelheid en de transpiratie van de behandelde bladeren gemeten. Na één dag werd een verhoging van de donkerademhaling gemeten in vergelijking met de controle. Vijtien dagen na behandeling werden verschillende resultaten gevonden in de twee experimentele jaren. Onder warme en droge omstandigheden in 1986 was de donkerademhaling oger terwijl de fotosynthese bij verzadigende lichtintensiteiten, de geleidbaarheid van het mesofyl en het stikstofgehalte van de bladeren lager waren dan in de controle. Ook werden chlorotische vlekken waargenomen. Bij gematigde temperaturen en relatieve vochtigheid in 1987 werd een verlaging van de initiële efficiëntie van lichtbenutting gemeten.In twee veldexperimenten werd een natuurlijke aantasting van voornamelijkS. avenae op verschillende tijdstippen chemisch bestreden. Op deze wijze werden aantastingen van verschillende omvang en duur verkregen. Vanaf bloei van het gewas werden wekelijks gewasmonsters geanalyseerd. Een natuurlijke aantasting vanaf DC 71 met een bladluisindex van 182 en een piekdichtheid van 15,8 bladluizen per halm, leidde niet tot significante reduktie van de gewasproduktie. Een aantasting beginnend in DC 71 met een bladluisindex van 544 en een piekdichtheid van 44,4 leidde tot significante verlaging van de bladoppervlakteïndex, de blad biomassa, de hoeveelheid water-oplosbare koolhydraten en het korrelgewicht. Geen effekten werden waargenomen op halm-en korreldichtheid of op het stikstofgehalte van plantedelen bij de oogst.     

Virulent and avirulent isolates of Pseudomonas syringae subsp. savastanoi as colonizers of olive leaves: evaluation of possible biological control of the olive knot pathogen1

The epiphytic survival of virulent and avirulent (indoleacetic acid-deficient mutants) isolates of Pseudomonas syringae subsp. savastanoi, and their ability to colonize the olive phylloplane, was monitored for up to 30 days after artificial inoculation of several olive cultivars. After an initial decrease in numbers, the virulent bacteria multiplied and established a potential inoculum on olive leaf surfaces. In contrast, the numbers of avirulent bacteria rapidly diminished, so that they were eventually no longer detectable. Under the conditions used in this study, none of the avirulent mutants (producers or non-producers of bacteriocins) were able to compete with or successfully to inhibit the virulent isolate in vivo. This was probably due to the lack of epiphytic multiplication of the avirulent mutants.