Some physicochemical factors influencing foliar uptake enhancement of glyphosatemono(isopropylammonium) by polyoxyethylene surfactants

Structure-concentration–foliar uptake enhancement relationships between commercial polyoxyethylene primary aliphatic alcohol (A), nonylphenol (NP), primary aliphatic amine (AM) surfactants and the herbicide glyphosatemono(isopropylammonium) were studied in experiments with wheat (Triticum aestivum L.) and field bean (Vicia faba L.) plants growing under controlled-environment conditions. Candidate surfactants had mean molar ethylene oxide (EO) contents ranging from 5 to 20 and were added at concentrations varying from 0·2 to 10 g litre^?-1 to [¹⁴C]glyphosate formulations in acetone–water. Rates and total amounts of herbicide uptake from c. 0·2–μl droplet applications of formulations to leaves were influenced by surfactant EO content, surfactant hydrophobe composition, surfactant concentration, glyphosate concentration and plant species, in a complex manner. Surfactant effects were most pronounced at 0·5 g acid equivalent (a.e.) glyphosate litre^?-1 where, for both target species, surfactants of high EO content (15–20) were most effective at enhancing herbicide uptake: surfactants of lower EO content (5–10) frequently reduced, or failed to improve, glyphosate absorption. Whereas, at optimal EO content, AM surfactants caused greatest uptake enhancement on wheat, A surfactants gave the best overall performance on field bean; NP surfactants were generally the least efficient class of adjuvants on both species. Threshold concentrations of surfactants needed to increase glyphosate uptake were much higher in field bean than wheat (c. 2 g litre^?-1 and < 1 g litre^?-1, respectively); less herbicide was taken up by both species at high AM surfactant concentrations. At 5 and 10 g a.e. glyphosate litre^?-1, there were substantial increases in herbicide absorption and surfactant addition could cause effects on uptake that were different from those observed at lower herbicide doses. In particular, the influence of EO content on glyphosate uptake was now much less marked in both species, especially with AM surfactants. The fundamental importance of glyphosate concentration for its uptake was further emphasised by experiments using formulations with constant a.i./surfactant weight ratios. Any increased foliar penetration resulting from inclusion of surfactants in 0·5 g litre^?-1 [¹⁴C]glyphosate formulations gave concomitant increases in the amounts of radiolabel that were translocated away from the site of application. At these low herbicide doses, translocation of absorbed [¹⁴C]glyphosate in wheat was c. twice that in field bean; surfactant addition to the formulation did not increase the proportion transported in wheat but substantially enhanced it in field bean.     

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.     

A simple diffusion model of the effect of droplet size and spread area on foliar uptake of hydrophilic compounds

The uptake of a hydrophilic active ingredient through the leaves of plants is mathematically modelled as a simple diffusion process. A three layer model is considered consisting of the droplet, the cuticle and the subcuticle. Translocation of the active ingredient from the subcuticle is allowed for as is depletion of the active ingredient from the droplet. Both the effect of the size of the droplets on the leaf surface and surfactant enhanced spreading of the droplet is examined. It is found that decreasing the size of the droplet leads to an increase in the percentage uptake of the active ingredient. Increasing the spread area of the droplet is found to increase the percentage uptake with the effect greatest in larger droplets.     

Factors affecting foliar retention of some model adjuvant oil-in-water emulsions

The foliar retention of dilute oil-in-water emulsions containing three chemical types of adjuvant oil formulated either as ECs or EWs was compared in track-sprayer experiments using the water-soluble tracer, fluorescein. Although both types of emulsion enhanced tracer deposition onto water-repellant pea and barley foliage, compared with sprays containing no adjuvant, consistently better retention was achieved using the EW emulsions, irrespective of oil composition. On young plants, fluorescein retention using the EC emulsifier alone was similar to that from the corresponding emulsions. However, on older plants, retention from EC emul-sions was superior to that from the EC emulsifier. Compar-able effects were not observed using the EW stabiliser, which had little influence on the efficiency of spray deposition. The retention behaviour of the various oil-based adjuvants is discussed in relation to their effects on spray quality and their formulation ingredients. © 1998 Society of Chemical Industry     

Development of a predictive uptake model to rationalise selection of polyoxyethylene surfactant adjuvants for foliage-applied agrochemicals

Composition-concentration relationships between a series of C₁₃/C₁₄ polyoxyethylene primary alcohol (AE) surfactants and the foliar uptake enhancement of five model neutral organic compounds were examined in factorially designed experiments on wheat (Triticum aestivum L.) and field bean (Vicia faba L.) plants grown under controlled environment conditions. Model compounds were applied to leaves as c.0.2-μl droplets of 0.5 g litre^?1 solutions in aqueous acetone in the absence or presence of surfactants at 0.2, 1 and 5g litre^?1. Uptake of the highly water-soluble compound, methylglucose (log octanol-water partition coefficient (P) = - 3.0) was best enhanced by surfactants with high E (ethylene oxide) contents (AE15, AE20), whereas those of the lipophilic compounds, WL110547 (log P = 3.5) and permethrin (log P = 6.5), were increased more by surfactants of lower E contents, especially AE6. However, there was little difference between AE6, AE11, AE15 and AE20 in their ability to promote uptake of the two model compounds of intermediate polarity, phenylurea (log P = 0.8) and cyanazine (log P = 2.1). Absolute amounts of compound uptake were also influenced strongly by both surfactant concentration and plant species. Greatest amounts of uptake enhancement were often observed at high surfactant concentration (5 g litre^?1) and on the waxy wheat leaves compared with the less waxy field bean leaves. The latter needed higher surfactant thresholds to produce significant improvements in uptake. Data from our experiments were used to construct a simple response surface model relating uptake enhancement to the E content of the surfactant added and to the physicochemical properties of the compound to be taken up. Qualitative predictions from this model might be useful in rationalising the design of agrochemical formulations.     

Effects of formulation with different adjuvants on foliar uptake of difenzoquat and 2,4-D: model experiments with wild oat and field bean

The effect of different adjuvants on the foliar uptake of difenzoquat methyl sulfate and sodium 2,4-D was studied in wild oat and field bean plants growing under controlled environmental conditions. The ¹⁴C-herbicides were applied to leaves as c. 0–2-μl droplets, usually containing 0.5 g 1^?1 active ingredient, plus adjuvants in the range 0.05–5 g 1^?1. The addition of non-ionic polyoxyethylene surfactants to solutions of both herbicides could induce considerable foliar uptake. Aliphatic C₁₃C₁₃ alcohol surfactants generally improved uptake more than nonylphenol surfactants when used at equivalent concentrations and ethylene oxide (EO) contents. The surfactant threshold for enhancement of difenzoquat uptake in wild oat was very low (0.05 g 1^?1), whilst that in field bean was much higher (>0.5 g 1^?1). For 2,4-D, surfactants at >0–5 g 1^?1 were needed to produce substantial increases in its uptake into both species. Although surfactants of low EO content (5–6) were less efficient at promoting difenzoquat uptake than those of higher EO content (10–20), particularly in wild oat, there was little dependence on surfactant EO content for enhancement of 2,4-D uptake. Adjuvants with humectant properties also promoted penetration of difenzoquat, but less so than alcohol or nonylphenol surfactants. For formulations of both ¹⁴C-herbicides translocation was directly related to the quantity of radiolabel that had penetrated the leaf tissue. Effets de la formulation avec différents adjuvants sur l'absorption foliaire du difenzoquat et du 2,4-D: modeles experimentaux sur la folle avoine et le haricot L'influence de differents adjuvants sur l'absorption foliaire du difenzoquat methyl sulfate et du 2,4 D sodium a eétéétudiée chez la folle avoine et le haricot, cultivés sous des conditions environnementales contrôlées. Les herbicides marquees au ¹⁴C ont ete appliquées aux feuilles sous forme de gouttelettes de 0,2 μl contenant 0,5 g 1^?1 de matière active, avec en plus des adjuvants de 0,05 à 5 g ^?1. L'adjonction de surfactants polyoxyethylénes non ioniques aux solutions des deux herbicides pourrait induire un absorption foliaire importante. Les surfactants d'alcools aliphatiques C₁₃/C₁₅ ont généralement augmenté la pénétration mieux que les surfactants de type nonylphénol utilises à une concentration équivalente et que les oxydes d'éthylènes (EO). Le seuil de surfactant pour l'amélioration de l'absorption de difenzoquat sur folle avoine était très bas (0,05 g 1^?1) tandis que sur haricot, il était beaucoup plus éievé (> 0,5 g 1^?1). Pour le 2,4 D, des surfactants à une dose de >0,5 g 1^?1 sont nécessaires pour produire une amelioration de son absorption chez les deux espéces. Bien que les surfactants à faible teneur en EO (5–6) fussent moins efficace pour favoriser l'absorption du difenzoquat que ceux a forte teneur (10–20), spécialement pour la folle avoine, il y avait une petite dépendance sur la teneur en EO pour l'amélioration de l'absorption du 2,4 D. Les adjuvants avec des propriétés d'humectation ont favorisé la pénétration du difenzoquat, mais moins que les surfactants alcool ou nonylphenol. Pour les formulations des deux herbicides marqués au ¹⁴C, le transport était directement reliéà la quantité de molécule marquée ayant pénétrée dans le tissu foliaire. Wirkung verschiedener Netzmittel auf die Blattaufnahme von Difenzoquat und 2,4-D am Beispiel von Flug-Hafer und Ackerbohne Der Einfluß verschiedener Zusatzstoffe auf die Blattaufnahme von Difenzoquat und 2,4-D-Na- Salz wurde an Flug-Hafer- und Ackerbohnen-Pflanzen unter kontroUierten Bedingungen untersucht. Die ¹⁴C-Herbizide wurden auf die Blatter mit etwa 0,2 μl großen Tröpfchen einer Lösung mit 0,5 g 1^?1 AS und 0,05 bis 5 g 1^?1 des Zusatzstoffs ausgebracht. Durch Zugabe von nichtionischen Polyoxyethylen-Netzmittein zu den Lösungen der beiden Herbizide konnte die Blattaufnahme erheblich gesteigert werden. Aliphatische C₁₃C₁₅-Alkohol-Netzmittel förderten die Aufnahme mehr als Nonylphenol-Netzmittel, wenn sie mit equivalenten Konzentrationen und Ethylenoxid-(EO)Gehalten ausgebracht wurden. Die Schwelle für die Steigerung der Difenzoquat-Aufnahme durch Netzmittel lag bei Flug-Hafer sehr niedrig (0,05 g 1^?1), bei der Ackerbohne vielhöher (>0,5 g 1^?1). Bei 2,4-D wurden bei beiden Arten zur deutlichen Förderung der Aufnahme Netzmittelkonzentrationen von >0,5 g 1^?1 benötigt. Obwohl Netzmittel mit niedrigem EO-Gehalt (5–6) die Difenzoquat-Aufnahme weniger förderten als solche mit höherem Gehalt (10–20). besonders bei Flug-Hafer, ergab sich für die Förderung der 2,4-D-Aufnahme kaum eine Abhängigkeit vom EO-Gehalt des Netzmittels. Additive mit feuchtigkeitshaltenden Eigenschaften förderten auch die Aufnahme von Difenzoquat, aber weniger als alkoholische oder nonylphenolische Netzmittel. Die Translokation der Mischungen der beiden ¹⁴C-Herbizide stand in direktem Verhäitnis zur Radioaktivitätsmenge, die in das Blattgewebe aufgenommen wurde.     

Effects of some nonionic polyoxyethylene surfactants on uptake of ethirimol and diclobutrazol from suspension formulations applied to wheat leaves

The influence of a number of commercial nonionic polyoxyethylene surfactants on the foliar penetration and movement of two systemic fungicides, ethirimol and diclobutrazol, was studied in outdoor-grown wheat plants at different growth stages and post-treatment temperatures in two consecutive growing seasons. Both fungicides were applied as ca 0·2 μl droplets of aqueous suspension formulations containing 0·5 g litre^?1 of ¹⁴C-labelled active ingredient; surfactants were added to these suspensions at concentrations ranging from 0·2-10 g litre^?1. To achieve optimum uptake of each fungicide the use of surfactants with different physicochemical properties was required. For diclobutrazol, a lipophilic compound, uptake of radiolabel was best with surfactants of low mean molar ethylene oxide (E) content (5-6) but it was necessary to use concentrations of ca 5 g litre^?1 to attain this. The surfactant threshold concentration for uptake enhancement of radiolabel from ethirimol formulations (< 2 g litre^?1) was much lower than that for diclobutrazol but surfactants with E contents > 10 induced the greatest amount of uptake. For both fungicides, surfactants with an aliphatic alcohol hydrophobe were generally more efficient in promoting their uptake than those with a nonylphenol moiety. The sorbitan-based surfactant ‘Tween 20’ proved to be an effective adjuvant only for the ethirimol formulation; the uptake enhancing properties of the block copolymer ‘Synperonic PE/F68’ were weak. Uptake performance could not be related to the spreading properties of the respective formulations on the wheat leaf surface or to differences in solubilisation of the two fungicides by the surfactants. Although surfactants could substantially increase the amount of acropetal transport of radiolabel from both fungicides, none of those tested specifically promoted it; a constant proportion of the radioactive dose absorbed by a treated leaf was usually exported away from the site of application. The results are discussed in the light of current theories about the mode of action of surfactants as spray adjuvants.     

Interactions of carotenoids with some organophosphorus insecticides

The interactions of some organophosphorus insecticides (OPI) with carotenoids from oranges were studied in vitro. In the initial step, 5,6-epoxy (di-epoxy) xanthophylls are isomerised to 5,8-furano (di-furano) xanthophylls. This reaction can also be brought about by hydrogen ions. Degradation products of OPI or impurities present in commercial samples may be acidic. Subsequent reactions lead to complete loss of the long wavelength chromophore.     

Modelling uptake into roots and subsequent translocation of neutral and ionisable organic compounds

A study on uptake of neutral and dissociating organic compounds from soil solution into roots, and their subsequent translocation, was undertaken using model simulations. The model approach combines the processes of lipophilic sorption, electrochemical interactions, ion trap, advection in xylem and dilution by growth. It needs as input data, apart from plant properties, log K_OW, pK_a and the valency number of the compound, and pH and chemical concentration in the soil solution. Equilibrium and dynamic (steady‐state) models were tested against measured data from several authors, including non‐electrolytes as well as weakly acidic and weakly basic compounds. Deviations from the measured values led to further development of the model approach: sorption in the central cylinder may explain the small transpiration stream concentration factor of lipophilic compounds. For non‐electrolytes, the model predicted uptake and translocation with high accuracy. For acids and bases, the tendency of the results was satisfactory. The dynamic model and the equilibrium approach gave similar results for the root concentration factor. The calculation of the transpiration stream concentration factor was more accurate with the dynamic model, but still gave deviations up to factor of ten or more. The dominating process for monovalent weak electrolytes was found to be the ion trap effect. © 2000 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.     

Effects of seed potato tuber treatment with imidacloprid on some soil and foliar insects in Croatia

The treatment of seed potato tubers by imidacloprid, as well as the standard granular insecticides applied in the furrow, did not, in four years of trials, sufficiently prevent damage from wireworms, noctuid larvae and mole crickets to potato tubers. The main reason for this failure is the spatial and temporal distance between the application of insecticides and the moment when their action is needed. On the other hand, the effects of imidacloprid applied as seed tuber treatment on the larvae of the Colorado potato beetle was very good: depending upon conditions, it lasted from at least 55, to 70 days at the most. It protected the foliage from any substantial damage from the entire first generation, and ensured high yields. Therefore a decision on seed tuber treatment with imidacloprid in Croatia should primarily depend upon the cost/benefit calculation based on damage expected from the CPB (or aphids), and not from soil insect pests.     

Effects of seed potato tuber treatment with imidacloprid on some soil and foliar insects in Croatia

The treatment of seed potato tubers by imidacloprid, as well as the standard granular insecticides applied in the furrow, did not, in four years of trials, sufficiently prevent damage from wireworms, noctuid larvae and mole crickets to potato tubers. The main reason for this failure is the spatial and temporal distance between the application of insecticides and the moment when their action is needed. On the other hand, the effects of imidacloprid applied as seed tuber treatment on the larvae of the Colorado potato beetle was very good: depending upon conditions, it lasted from at least 55, to 70 days at the most. It protected the foliage from any substantial damage from the entire first generation, and ensured high yields. Therefore a decision on seed tuber treatment with imidacloprid in Croatia should primarily depend upon the cost/benefit calculation based on damage expected from the CPB (or aphids), and not from soil insect pests.     

Interactions between organophosphorus compounds and soil materials I. Adsorption of ethyl methylphosphonofluoridate by clay and organic matter preparations and by soils

Data for the adsorption of ethyl methylphosphonofluoridate from aqueous and the vapour phases onto montmorillonite and kaolinite clays, onto soil organic matter preparations, and onto a limited number of soils are reported. These show that the phosphonofluoridate was absorbed from the vapour phase onto the dry clay preparations by physical-chemical forces but was not adsorbed by the organic soil materials. In a general way adsorption onto dry soils could be related to their clay contents when the organic matter contents were low. Water was found to compete effectively with the phosphonofluoridate for adsorption sites, and it is concluded that this molecule will be most effectively retained by dry soils low in organic matter and rich in clay. Mechanisms for its adsorption onto clays are discussed.     

A numerical study of combined use of two biocontrol agents with different biocontrol mechanisms in controlling foliar pathogens

Effective use of biocontrol agents is an important component of sustainable agriculture. A previous numerical study of a generic model showed that biocontrol efficacy was greatest for a single biocontrol agent (BCA) combining competition with mycoparasitism or antibiosis. This study uses the same mathematical model to investigate whether the biocontrol efficacy of combined use of two BCAs with different biocontrol mechanisms is greater than that of a single BCA with either or both of the two mechanisms, assuming that two BCAs occupy the same host tissue as the pathogen. Within the parameter values considered, a BCA with two biocontrol mechanisms always outperformed the combined use of two BCAs with a single but different biocontrol mechanism. Similarly, combined use of two BCAs with a single but different biocontrol mechanism is shown to be far less effective than that of a single BCA with both mechanisms. Disease suppression from combined use of two BCAs was very similar to that achieved by the more efficacious one. As expected, a higher BCA introduction rate led to increased disease suppression. Incorporation of interactions between two BCAs did not greatly affect the disease dynamics except when a mycoparasitic and, to a lesser extent, an antibiotic-producing BCA was involved. Increasing the competitiveness of a mycoparasitic BCA over a BCA whose biocontrol mechanism is either competition or antibiosis may lead to improved biocontrol initially and reduced fluctuations in disease dynamics. The present study suggests that, under the model assumptions, combined use of two BCAs with different biocontrol mechanisms in most cases only results in control efficacies similar to using the more efficacious one alone. These predictions are consistent with published experimental results, suggesting that combined use of BCAs should not be recommended without clear understanding of their main biocontrol mechanisms and relative competitiveness, and experimental evaluation.     

Interplay of apple volatile organic compounds with Neofabraea vagabunda and other post-harvest pathogens

Neofabraea vagabunda, causing bull’s eye rot, produces notable loss during cold storage of apples growing in cool humid regions. The infection initiates in the orchard, but the pathogen lives quiescently in fruit for some months before causing the symptoms of the disease. In vivo and in vitro assays were carried out to gain knowledge on the influence of fruit volatile organic compounds (VOCs) in N. vagabunda development and define volatile markers for pathogen detection, using SPME/GC-MS, PTR-ToF-MS analysis and light microscopic observations. This study reports that: (i) the main VOCs of Cripps Pink apple (highly susceptible to bull’s eye rot) are degraded during the conidial germination of N. vagabunda, stimulating pathogen hyphal growth towards the host; (ii) first disease symptoms appear when fruit releases VOCs related to senescence, which also stimulate pathogen hyphal growth; (iii) VOCs typical of ripe-senescent fruit are also emitted by infected fruit during N. vagabunda quiescence, and methanol and ethanol are the earliest markers of bull’s eye rot; and (iv) the in vitro volatile metabolism of Botrytis cinerea, Penicillium expansum and Colletotrichum fioriniae has similarities with that of N. vagabunda, but the volatile profile of each pathogen is distinguishable. Overall, this study provides novel knowledge on fruit–fungus interaction and insights for the development of tools for early disease detection in packing houses.     

Effect of foliar applications of some insecticides onBemisia tabaci, predators and parasitoids: Implications in its management in Pakistan

Three experiments were carried out during three consecutive years to evaluate 19 insecticides and 12 tank mixtures of different groups of insecticides against the whiteflyBemisia tabaci and its predators and parasitoids under field conditions in cotton. In the first experiment, the whitefly population was lower in treatments with thiacloprid and higher in those with black warrant (a.i. alcohol) and cypermethrin; the number of predators was higher with Agri-50 and spinosad and lowest with cypermethrin, whereas percent parasitism was higher with thiacloprid and lower with methamidophos. In the second experiment, the whitefly population was lower in treatments with buprofezin, pyriproxyfen and diafenthiuron and higher in those with endosulfan, imidacloprid and thiamethoxam; the number of predators was higher with pyriproxyfen and lower with thiamethoxam, whereas percent parasitism was higher with pyriproxyfen and lower with thiamethoxam. In the third experiment, the whitefly population was lower in a treatment mixture with buprofezin + fenpropathrin and higher in that with thiamethoxam + chlorpyrifos; the number of predators was higher with buprofezin + fenpropathrin and lower with deltamethrin + triazophos and deltamethrin + chlorpyrifos, whereas percent parasitism was higher with the mixture of pyriproxyfen + chlorpyrifos and lower in imidacloprid + chlorpyrifos, betacyfluthrin + triazophos, and deltamethrin + triazophos. Effective use of these insecticides to manage whitefly infestations and to save predators and parasitoids is discussed. http:www.phytoparasitica.org posting August 7, 2008.     

Sorption of ionisable organic compounds by field soils. Part 1: Acids

Sorption of different classes of weak organic acids was measured using soils with a range of pH values, taken from long-term field experiments that had received different amounts of lime. Non-ionisable compounds were used to demonstrate that the soils of different pH used in the experiments have similar sorptive properties. Values of the sorption coefficients for chloride ion were negative at all pHs except one. Sorption of moderately polar, monobasic, weak acids was weak in acidic soils and very weak in neutral and alkaline soils where they were predominantly dissociated. A lipophilic weak acid was strongly sorbed even at high pH. A model is presented which estimates soil/water distribution coefficients, at any soil pH, from lipophilicity and pK_a of the acid and organic matter content of the soil. The model was derived using sorption measured for substituted phenoxyacetic acids. Sorption values calculated using the model were compared with values measured for chlorsulfur on and showed useful agreement. Dibasic acids were strongly sorbed, probably by the mechanism of ligand exchange, if they were chelating agents with potential to form 5- or 6-membered rings with an acceptor atom. Phenylphosphonic acid was strongly sorbed, being a strong monodentate ligand.     

Rates of reaction of singlet oxygen with some systemic pyrimidine fungicides and related compounds

Rate constants have been measured for the reaction in chloroform solution of singlet oxygen with the fungicides ethirimol (5-butyl-2-ethylamino-6-methylpyrimidin-4-ol) and dimethirimol (5-butyl-2-dimethylamino-6-methylpyrimidin-4-ol), and with the compounds 2-dimethylamino-5,6-dimethylpyrimidin-4-ol, 2-dimethylamino-6-methylpyrimidin-4-ol, 4-benzyloxy-2-dimethylamino-5,6-dimethylpyrimidine and 2-diethylamino-6-methylpyrimidin-4-ol. The values obtained show that singlet oxygen reacts readily with these compounds; the differences between the rate constant values have been rationalised in terms of the different structural features of the compounds studied. The possibility that singlet oxygen may react with agricultural chemicals under natural conditions is considered.