A compartmental computer model of foliar uptake of pesticides

The uptake and movement of a chemical into a wheat leaf has been simulated in a 5-compartment model. The compound is considered to be applied to the leaf as discrete droplets of solution, from which water evaporates at a uniform rate. Solute diffuses from the droplets through the plant cuticle into the epidermal cell wall, and from there either into and out of the cytoplasm and vacuole of the mesophyll cells or along cell walls to the xylem. Once in the xylem it is carried in the transpiration stream towards the tip of the leaf. Accurate values for the parameters required by the model have not yet been measured, but the model simulates in a qualitative manner the movement pattern observed for 1-methyl-2-pyridone. The results presented focus attention on the possible importance of membrane permeability in determining the phytotoxicity of xylem mobile pesticides.     

Control of foliar diseases in barley: towards an integrated approach

Barley is one of the world??s most important crops providing food and related products for millions of people. Diseases continue to pose a serious threat to barley production, despite the use of fungicides and resistant varieties, highlighting the impact of fungicide resistance and the breakdown of host plant resistance on the efficacy of control measures. This paper reviews progress towards an integrated approach for disease management in barley in which new methods may be combined with existing measures to improve the efficacy of control in the long-term. Advances have been made in genetic mapping of resistance (R) genes and in identifying novel sources of genes in wild barley populations and land races. Marker assisted selection techniques are being used to pyramid R genes to increase the durability of resistance. Elicitors to induce host resistance used in combination with fungicides can provide effective disease control in the field and could delay the evolution of fungicide insensitivity. Traits that may contribute to disease tolerance and escape have been identified and the extent of genetic variation within barley germplasm is being determined. Tools are being developed to integrate the above methods via an assessment of the risk of economic injury occurring from disease to guide decisions on the requirement for fungicide treatment. Barriers exist to the adoption of integrated management approaches from growers and end-users further down the supply chain (e.g. acceptance of variety mixtures) and policy incentives from government may be required for it to be taken up in practice.     

The foliar uptake of isoproturon by wheat and Alopecurus myosuroides huds

The uptake and translocation of ¹⁴C-isoproturon (3-p-cumenyl-1-1,-dimethylurea) in wheat (tolerant) and backgrass (sensitive) following foliar treatment under controlled environmental conditions were examined. The amount of ¹⁴C-isoproturon translocated through the xylem was about 10 times that translocated through the phloem in both wheat and blackgrass. However, 25.5% of the applied ¹⁴C-isoproturon was translocated in the xylem in blackgrass, compared with 8.9% in wheat. ¹⁴C-isoproturon did not respond significantly to induced sink-demand in either species. Leaf-disc autoradiograms revealed the absorption of ¹⁴C-isoproturon by the minor veins and translocation into the cut vein endings. No significant differences were found in between wheat and blackgrass in this respect.     

Benzimidazole pesticides: Analysis and transformations

Some properties, analysis and transformations by plants, animals, soil and light of benomyl, carbendazim, thiabendazole, fuberidazole, cypendazole and fenazaflor are discussed.     

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.     

Spray retention, foliar uptake and translocation of glufosinate and glyphosate in Ambrosia artemisiifolia

Ambrosia artemisiifolia plants exhibit stomata on both leaf surfaces and three types of trichomes: (i) small (<50 μm) spherical or ovoid, (ii) medium‐sized (50–100 μm) and (iii) long (100–200 μm) and sharp. Only the long and sharp trichomes were stained with AgNO₃, indicating the presence of hydrophilic domains. Epicuticular waxes appeared amorphous, consistent with high levels of spray retention. Glufosinate was readily taken up by A. artemisiifolia leaves, with maximum uptake of >80% of the applied label, and half maximum uptake being reached within 6 h. The foliar uptake of glyphosate was nearly complete and half of it was attained after 3 h. Glufosinate and glyphosate were ambimobile and their translocation out of the treated leaves amounted to 13–16% and 11–15% of the absorbed radioactive label respectively. Glufosinate was mainly directed to the apical developing tissues, with less amounts reaching the tissues below the treated leaves. Glyphosate was directed towards the sink tissues (apical developing tissues and roots). The sensitivity of A. artemisiifolia to glufosinate and glyphosate can be explained by high spray retention, rapid and important foliar uptake, and appreciable migration out of the parts of the plant hit by the spray.     

Influence of wetting agents on the foliar uptake and herbicidal activity of glufosinate

The influence of four different wetting agents on the foliar retention, uptake and herbicidal activity of the glutamine synthetase inhibitor, glufosinate, was examined in growth-chamber experiments on barley (Hordeum vulgare L. cv Roland) and barnyard grass (Echinochloa crus-galli (L.) P.B.) as test species. The non-formulated monoammomum salt, glufosinate-ammonium, was applied as a spray, either alone or mixed with a wetting agent. The dose rates of herbicide and wetting agent were 0.5 g a.i. litre^?1 and 2.0 g litre^?1, respectively, on barnyard grass, and 2.0 g a.i. litre^?1 and 60 g litre^?1, respectively, on barley. Herbicide damage, rated 10 days after spraying, was greatest when glufosinate was used with a sodium C₁₂/C₁₄-alcohol-diglycolether sulfate (FAEO-sulfate) and least with polyoxyethylene (POE)(8) tridecyl ether; intermediate effectiveness was obtained with a combination of herbicide and a POE(15) tridecyl ether or POE(15)-tallow amine. The activity of the target enzyme, glutamine synthetase, measured 2 h after spraying, was reduced most when FAEO-sulfate was present and least with POE(8) tridecyl ether. The behaviour of the glufosinate wetting agent solutions on plant foliage was analysed by measurements of spray retention, droplet contact angles and foliar uptake of [¹⁴C]glufosinate. The results led, for both grass species, to the conclusion that differential ability of the wetting agents to enhance the permeation of glufosinate from the leaf surface deposit into the leaf tissue was the main factor responsible for the differences in herbicidal effectiveness of the glufosinate/wetting agent combinations used in this study.     

A scanning electron microscope study of glyphosate deposits in relation to foliar uptake

The effects of several formulations on foliar uptake of glyphosate, and on the morphology of glyphosate deposits on leaves, were examined in Tartary buckwheat (Fagopyrum tataricum (L.) Gaertn.). [¹⁴C]glyphosate, in the form of the free acid or the isopropylamine salt (IPAS), was applied to foliage alone or with various adjuvants. Uptake of all glyphosate IPAS formulations was greater than that of the corresponding acid formulation. Addition of ‘Tween 20’ enhanced the uptake of glyphosate IPAS compared to glyphosate alone, but had no effect on the uptake of glyphosate acid. Ammonium sulfate and the ‘Roundup’ formulation blank increased the uptake of glyphosate acid and IPAS to 2-3 times that of herbicide alone. Surface deposits, as observed by scanning electron microscopy, varied with the formulation of the herbicide, although there were no differences between the acid and IPAS formulations. Glyphosate alone initially formed a deposit with both crystalline and smooth, amorphous areas. Later in the treatment period (48 and 72 h after application), the deposit was almost entirely crystalline. The addition of ‘Tween 20’ or of formulation blank resulted in the formation of a more amorphous, non-crystalline deposit. Herbicide solutions containing ammonium sulfate dried to form a highly crystalline deposit. However, crystals similar to those of glyphosate alone were not visible in these deposits. The ability of these adjuvants to prevent or delay crystal formation may play a role in their enhancement of herbicide uptake.     

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.     

Contributions of stomatal infiltration and cuticular penetration to enhancements of foliar uptake by surfactants

Radiolabelled deoxyglucose (DOG) and glyphosate were used to investigate the effects of certain non-ionic surfactants on the kinetics of foliar uptake in three species. ‘Silwet L-77’ (5 g litre^?1), an organosilicone surfactant, enabled spray solutions to infiltrate stomata, providing uptake of DOG into Vicia bean (50%), oat (35%) and wheat (20%) within 10 min of application. ‘Silwet Y-12301’, another organosilicone, also induced stomatal infiltration but to a lesser extent; unlike L-77, this was attenuated by partial stomatal closure. A third organosilicone, ‘Silwet L-7607’, and two conventional surfactants, ‘Triton X-45’ (OP5) and ‘Agral 90’ (NP9), did not induce stomatal infiltration. The effective minimum concentration of L-77 required to enable infiltration of stomata was 2 g litre^?1. The uptake of glyphosate into bean did not differ from that of DOG but the ‘Roundup’ formulation of glyphosate partially antagonised the infiltration provided by L-77. Addition of surfactants did not increase the rate of cuticular penetration of DOG into bean but total uptake was increased, except by NP9, either via infiltration (L-77 and Y-12301) or by extending the period during which penetration occurred (L-7607 and OP5). The surfactants had a variable effect on rates of penetration of DOG into wheat and oat. In general, foliar uptake followed an exponential timecourse which was largely complete within 6 h and only rarely approached 100% of the applied chemical. The stomatal infiltration provided by L-77 caused an increase in translocation of DOG in bean.     

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.     

Relationships between lipophilicity and root uptake and translocation of non-ionised chemicals by barley

The uptake by roots from solution, and subsequent translocation to shoots in barley, of two series of non-ionised chemicals, O-methylcarbamoyloximes and substituted phenylureas, were measured, Uptake of the chemicals by roots was greater the more lipophilic the chemical, and fell to a lower limiting value for polar chemicals. Translocation to the shoots was a passive process, and was most efficient for compounds of intermediate polarity. Both processes had reached equilibrium within 24h of treatment. The reported behaviour of many pesticides in various plant species agrees with the derived relationships, but the detailed mechanisms of these processes are unknown.     

Physico-chemical factors affecting uptake by roots and translocation to shoots of weak acids in barley

The uptake from solution of maleic hydrazide, flamprop and a series of phenoxyacetic acids by roots, and their subsequent translocation to shoots, was measured in barley. Both uptake and translocation increased as the pH of the solution decreased, the magnitude of the change varying amongst the chemicals tested. Uptake by roots could be accounted for by the ion-trap mechanism, which assumes that entry of the chemicals occurs largely by passive diffusion of the undissociated form of the acids, with passage of the anions across the cell membranes being very slow. The ratio of the permeability of the cell membranes to the undissociated and dissociated forms of the acids was estimated from the accumulation in roots, and in the phenoxyacetic acid series this ratio was maximal (4×10⁵) for compounds of intermediate lipophilicity. Maleic hydrazide and flamprop had much lower ratios, 1.8×10² and 10³ respectively; the value for flamprop was much less than for phenoxyacetic acids of similar lipophilicity, such as 2, 4- dichlorophenoxyacetic acid, indicating that lipophilicity may not be the sole factor determining the behaviour of weak acids in plants. Translocation to shoots was approximately proportional to the chemical concentrations in the roots.     

Studies on the abilities of uptake and translocation from root to shoot of pesticides in soil

The uptake experiments with pesticides were performed to clarify differences among plant species, and the influence of growth stages and conditions on the uptake and translocation ability of pesticides. There were 2–10-fold differences among plant species in the root and shoot concentrations of each pesticide, and shoot concentrations of pesticides in Brassica rapa L. var. perviridis were relatively high. In addition, the changes in shoot concentrations with growth stage of B. rapa were affected by root system development. The influence of temperature on uptake and translocation ability differed for each pesticide, while uptake and translocation ability were high for short day lengths. This indicated that plant uptake and translocation of pesticides were affected by root system development and growth conditions such as temperature and day length, not only the relationships to the chemical’s properties and behavior of organic chemicals in the soil.     

Control of loose smut (Ustilago nuda and U. tritici) infections in barley and wheat plants by foliar application of triadimefon

Foliar application of the broad-spectrum systemic fungicide triadimefon to loose smut-infected plants of wheat and barley produced a marked curative effect. Triadimefon was particularly effective when applied at the beginning of and during stem extension. In addition to reducing percentage plant infection, foliar application of this fungicide (particularly prior to flag leaf emergence) resulted in an increased proportion of infected ears which were only partially smutted. The curative effect of these early fungicide applications resulted in significant yield increases, as a consequence of increased grain number per m². Application of triadimefon to crops at ear emergence had no significant effect on percentage plant infection but resulted in lower levels of re-infection following artificial or natural inoculation of healthy ears, apparently as a result of a protectant effect of fungicide residues on or in the ovaries.     

Physicochemical factors affecting the uptake by roots and translocation to shoots of amine bases in barley

The uptake by barley roots from nutrient solution and subsequent transport to shoots of two series of amine bases were measured over 6 to 72 h. The compounds were chosen to span systematically ranges of lipophilicity (assessed using 1-octanol/water partition coefficients, K_ow) and pKa that would include commercial pesticide amines. In a series of six substituted phenethyl amines, strong bases with pKa∽9·5, all the compounds were strongly taken up by roots from solutions of pH 8·0; uptake declined substantially as the pH was lowered to 5·0, especially for the compounds of intermediate lipophilicity (log K_ow 2 to 3). This uptake could be ascribed to three processes: (i) accumulation of the cation inside the root cells due to the negative charge on the plasmalemma, as given by the Nernst equation and important only for the polar compounds which have low permeation rates through membranes; (ii) accumulation into the vacuole by ion-trapping, which was the dominant process at high pH for all compounds and at all pH values for the compounds of intermediate lipophilicity; (iii) partitioning on to the root solids, substantial only for the most lipophilic compounds. Translocation to shoots was proportional to uptake by roots, this ratio being independent of external pH for each compound and being optimal for the compounds of intermediate lipophilicity. Such proportionality was also observed in a series of three weaker bases of intermediate lipophilicity, in which compounds of pKa 7·4 to 8·0 were also well taken up and translocated whereas the very weak base 4-ethylaniline (pKa 5·03) was much less so. Tests with quaternised pyridines confirmed that organic cations move only slowly through membranes. The observed behaviour of the amines could be modelled reasonably well assuming that transport within the plant was dominated by movement across membranes of the non-ionised species, and this appeared to be true even for the most lipophilic phenethylamine (log K_ow 4·67) studied, though its long-distance movement would be as the protonated species. © 1998 Society of Chemical Industry     

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.     

The effect of the annual use of pesticides on soil microorganisms,pesticide residues in the soil and barley yields

A study has been made of the influence of pesticides used annually on soil microorganisms and crop yields. The persistence of these pesticides in the soil was also investigated. The herbicides MCPA, glyphosate, maleic hydrazide and tri-allate, and the insecticide parathion, were applied on experimental plots on which barley was grown during the years 1973-1981. The fungicide 2-methoxyethylmercury chloride was used every year for dressing the seeds grown in pesticide-treated plots. The pesticide treatments did not affect significantly the numbers of several groups of soil microorganisms. A slight increase was, however, observed in the nitrification activity in the soil. The barley yields were on average higher on pesticide-treated plots than on controls because of successful weed control. Pesticide residues in the soil were generally very low; for example, for parathion they were below 0.02 mg kg^?1 within 11 days, and for MCPA 0.06 mg kg^?1 within 7 days. However, the glyphosate residue was 1.6 mg kg^?1 in the autumn 2 days after the treatment, and the residue settled to a level of 0.2 mg kg^?1 during the following summer. No clear dependence was observed between the residue level and the time between treatment and sampling.     

Relationships between lipophilicity and the distribution of non-ionised chemicals in barley shoots following uptake by the roots

Determinations were made of the distribution of two series of non-ionised chemicals, ^O-methylcarbamoyloximes and substituted phenylureas, in barley shoots, following uptake by the roots from solution. The concentrations in basal and central shoot sections became constant after 24 to 48 h for all but the most lipophilic chemical studied, and were then greatest for the more lipophilic chemicals. Amounts in the leaves generally increased up to 72 or 96 h, when degradation balanced translocation. The accumulation of chemical in the lower section of shoots can be ascribed to a partitioning process similar to that in roots, the chemical being partitioned between the shoot and the xylem transpiration stream; this uptake could be estimated from the octan-1-01/water distribution coefficients, and was predicted to be greatest for compounds for which log K_ow=4. 5.