Influence of transport on gas loss from freight containers under fumigation. Part I: Experimental investigation

The rate of gas interchange between the atmosphere within a freight container and the external air has an important influence on the effectiveness of in-container fumigation. When a container is exposed to the wind or is in motion, the rate of gas interchange may be much greater than that under static conditions. The effect of motion or wind on gas interchange was studied by observing gas loss from freight containers, both empty and loaded with rice, while stationary and while being transported by rail. The gas interchange rate was determined by measuring the rate of loss from the containers of either a combination of a fumigant, methyl bromide, and a relatively inert tracer gas, carbon monoxide, or of carbon monoxide alone. In loaded containers the difference between the loss rate constants of methyl bromide and carbon monoxide (0.29.0.03d^?1) was within the range expected for the reaction of methyl bromide with rice. After allowing for gas loss caused by changes in temperature and pressure, the component of the interchange rate constant attributable to air motion was found to be proportional to gas-tightness as measured by a steady-state pressure test, and also to the relative air speed over the container. Under conditions of varying wind and train speed, the fraction of the initial concentration of gas remaining was found to be an exponential function of wind run past the container. When wind effects were not important, it was found to be an exponential function of distance travelled.     

Studies into the action of the diphenyl ether herbicides acifluorfen and oxyfluorfen. Part II: The interaction with photosynthetic electron transport reactions

The effects of acifluorfen and oxyfluorfen on photosynthetic electron transport reactions of pea chloroplasts were compared with those induced by paraquat and monuron. Monuron inhibited electron flow between photosystems I and II, and paraquat acted as an electron acceptor for photosystem I, promoting superoxide formation by illuminated chloroplasts. Neither acifluorfen nor oxyfluorfen at concentrations up to 50 μM affected non-cyclic electron flow or promoted superoxide formation. Both herbicides were shown to repress ferredoxin-dependent NADP⁺ reduction by illuminated chloroplasts. Further experiments showed that, in the presence of ferredoxin-NADP⁺ reductase and chloroplast membranes maintained in the dark, p-nitro diphenyl ether (DPE) herbicides promoted the rate of ferredoxin-dependent oxidation of NADPH, implying that these herbicides can accept electrons from reduced ferredoxin. The interaction between acifluorfen, ferredoxin and chloroplast membranes was examined further by following the effect of this herbicide on the peroxidation of illuminated thylakoids. Lipid peroxidation was promoted by acifluorfen, although this effect was abolished if thylakoids were washed prior to use. The effect of washing could be reversed by adding exogenous ferredoxin. These data demonstrate that interaction of DPE herbicides with photosynthetic electron transport in the vicinity of ferredoxin is necessary for light-dependent herbicide activation.     

肥液浓度对膜孔单向交汇入渗水分运移特性的影响

通过清水与不同肥液浓度的膜孔单向交汇室内入渗试验,研究了不同浓度的膜孔肥液单向交汇入渗量、湿润锋运移距离及土壤含水量分布.提出了土壤入渗量和湿润锋运移距离随肥液浓度的增加而增大的规律;建立了不同肥液浓度膜孔入渗量和湿润锋运移距离经验模型.经实测资料验证,模型精度较高;肥液浓度越大,相同时间的湿润锋运移距离越大,相同深度处的土壤含水量也越大.     

Synthesis and insecticidal activity of lipophilic amides. Part 5: Influence on activity of varying the substituent on nitrogen

Isomerisation or shortening of the 2-methylpropyl group in (2-methylpropyl)-6-phenylhexa-2, 4-dienamide lowers insecticidal activity, as does methylation at nitrogen. Methylation at each carbon atom in turn, and, within limits, in combination, gives compounds with substantial, sometimes increased, activity. Cyclic and olefinic equivalents of the effective alkyl substituents are mostly less active.     

Action of pesticides on earthworms. Part II: Elimination of parathion by the earthworm Eisenia foetida (Savigny)

The earthworm, Eisenia foetida, eliminated parathion and carbofuran at first order rates when continually rinsed in water after treatment with the pesticides. This experiment was also carried out on Lumbricus rubellus for comparison. Carbofuran which is more soluble in water, was eliminated quicker than parathion. The later rate of elimination was very similar for the two species, but immediately after injection the rate was much higher in E. foetida. The metabolism of 1-ethyl¹⁴C labelled parathion and paraoxon (diethyl 4-nitrophenyl phosphate) was studied in E. foetida. The worm was able to convert parathion to paraoxon by a rather slow process although this metabolite could not be detected in the worms due to its rapid transformation to diethyl hydrogen phosphate. Indirectly, paraoxon can be postulated as a parathion metabolite because of a progressive depression of cholinesterase level observed after treatment with parathion. Small amounts of diethyl hydrogen phosphate were detected as a metabolite of parathion; this is also an indication of paraoxon formation. During the 30 h following injection of parathion, only 4.4% of the applied dose was recovered as water-soluble metabolites (2.8% in the worms and 1.6% in the sand surrounding them), while 52% was recovered as unmetabolised parathion. Because of inefficient injection, only 70-59% of the dose thought to be injected was recovered. Therefore the part of the actual applied dose that remained unmetabolised was probably even greater (88%). Five days after injection of parathion, 15 and 9.3 % of the recovered radioactivity in the surrounding sand and in the worm extracts, respectively, was identified as O,O-diethyl O-hydrogen phosphorothioate, 3.7 and 7.0% as diethyl hydrogen phosphate, 8.8 and 3.3% as O-ethyl O-4-nitrophenyl O-hydrogen phosphorothioate (desethylparathion) and/or O-4-aminophenyl O,O-diethyl phosphorothioate, while 70.3 and 80.4% was unmetabolised parathion. Paraoxon was very quickly hydrolysed to diethyl hydrogen phosphate in vivo and in vitro. The in-vitro hydrolysis was associated with a microsomal fraction and was not inhibited by ethylenediaminetetra-acetic acid or 4-(chloromercuri)benzoic acid, and incompletely by aldicarb. Cholinesterase and arylesterase were therefore excluded as enzymes responsible for the activity.     

The degradation of diflubenzuron and its chief metabolites in soils. Part II: Fate of 4-chlorophenylurea

The fate of 4-chlorophenylurea in soils was studied with two preparations: one labelled with ¹⁴C in the phenyl ring and the other in the carbonyl group. The initial dose of 1 mg kg^?1 decreased to 50% in about 5 weeks in aerobic sandy clay and in about 16 weeks in anaerobic hydrosoil. Soil treatment with each of the preparations resulted in the release of [¹⁴C]carbon dioxide, pointing to decarbonylation and ring opening. The fraction of non-extractable (soil-bound) radioactivity increased during incubation. Quantities of ring-¹⁴C-labelled and carbonyl-¹⁴C-labelled bound residues differed strongly in the aerobic soil but only slightly in the anaerobic hydrosoil. It is assumed that two sorts of bound residues are formed from 4-chlorophenylurea: one is fairly stable and might consist of bound 4-chloroaniline or its transformation products, whereas the other is presumed to be a degradable derivative of 4-chlorophenylurea.     

Persistence of organochlorine insecticides on different substrates under different environmental conditions. I. The rates of loss of dieldrin and aldrin by volatilisation from glass surfaces

The losses of dieldrin and aldrin by volatilisation from crystalline deposits on glass surfaces in different environments were studied by using these insecticides labelled with the radioactive isotope ³⁶CL as a tracer. Volatilisation rates were very sensitive to changes in temperature and to a lesser extent to air movement, but not to change in relative humidity (the effect of which was measurable only on porous glass surfaces). All rates of loss from glass surfaces could be described mathematically in terms of single or double exponential equations, although many were better described by simple sigmoid (logistic) equations.     

Hydrolysis of cyanazine and related diaminochloro-1,3,5- triazines. Part II: hydrolysis in sulphuric acid solutions

Hydrolysis of cyanazine in sulphuric acid solutions involves primary attack at the nitrile group to give first the corresponding amide and then the carboxylic acid followed subsequently by displacement of the chlorine atom. Comparison of the respective reaction rates showed that, in sulphuric acid solutions (at concentrations around 0.5_M) at 25°C, the rate of this attack at the nitrile group is approximately ten times faster than at the chlorine atom. The kinetic data indicate that in these moderately acid solutions the mechanism of cyanazine hydrolysis corresponds to an A-2 reaction involving prior protonation of the nitrile group followed by rate determining nucleophilic attack by water. However, at higher acidities, the rates decelerate which leads both to diversion from the Zucker-Hammett postulate for simple A-2 reactions and to undue curvature in the Bunnett or Bunnett-Olsen linear free-energy plots, so that with the present data such a conclusion cannot be extended to the reaction in solutions of acidity higher than 0.5_M. Removal of the chlorine atom attached to the 1,3,5-triazine ring in atrazine was also found to be an A-2 reaction in moderately acid solutions, but at higher acidities ([H⁺]>2_M), there is an acceleration in the rate. It is suggested that this is a consequence of diprotonation of the diamino-1,3,5-triazine molecule.     

Studies of the mechanism of action of asulam in plants. Part II: Effect of asulam on the biosynthesis of folic acid

The possible relationship between folate levels in plants and their tolerance to asulam has been examined. Plants with a high content of folates were relatively less susceptible to asulam. There was evidence of a depletion of the folates in the shoots of plants treated with asulam, either alone at 1. 1 kg ha^?1 or in combination with 4, 6-diamino-1-(3, 4-dichlorophenyl)-1, 2-dihydro-2, 2-dimethyl-1, 3, 5-triazine (DCDT) at 1.1 kg ha^?1. In wheat shoot tips (Triricum estivum L.), asulam at 1.1 kg ha^?1 reduced the levels of the N⁵-methyl, N¹⁰-formyl and N⁵-formyl derivatives of 5, 6, 7, 8-tetrahydrofolates, particularly when applied in combination with DCDT. Studies with cell-free extracts of wheat seedlings revealed that asulam inhibited the enzymic synthesis of 7, 8-dihydro-pteroateina manner similar to sulphanilamide inhibition. The biochemical site of action of asulam in plants is discussed.     

肥液浓度对膜孔单向交汇入渗NO-3-N运移特性的影响

通过室内入渗试验,研究了不同浓度的膜孔肥液单向交汇入渗NO3--N的分布特性。研究表明,不同肥液浓度的膜孔入渗湿润体膜孔中心和交汇界面中心垂向土壤NO3--N的浓度锋运移距离与土壤水分运动的湿润锋一致;肥液浓度越大,相同入渗时间的NO3--N浓度锋运移距离越大,土壤NO3--N浓度最大值越大,相同深度处土壤NO3--N浓度也越大。建立了肥液交汇入渗湿润体膜孔中心和交汇界面中心垂向土壤NO3--N浓度分布特征与湿润体深度之间的分段函数模型,经实测资料验证表明,该模型精度较高。入渗供水过程中,NO3--N浓度锋运移距离和浓度最大值随时间的延长而增大;再分布过程中,NO3--N浓度前锋运移距离随时间延长而增大,而NO3--N浓度最大值逐渐减小。     

Assessment of a mathematical model to predict spray deposition under laboratory track spraying conditions. II: Examination with further plant species and diluted formulations

Mean spray depositions onto leaves of five plant species (Zea mays L., Vicia faba L., Sinapsis alba L., Glycine max (L.) Merr, Vitis vinifera L.) were measured following spraying of an array of 36 solutions of acetone + aqueous “Triton X-100” varying systematically in composition and properties. The spraying was carried out on five occasions using a standard laboratory track sprayer delivering the equivalent of 600 litre ha^?1 onto a plane surface around plant height. The results, plotted as response surfaces, showed that there was little variation in spray deposition with solution composition for V. vinifera, there were some slight decreases in deposition with increase in “Triton X-100” concentration on V. faba and S. alba, though not with increase in acetone concentration, and that there were slight systematic increases for G. max and large systematic increases for Z. mays with increase in acetone and “Triton X-100” up to concentrations of 350 ml litre^?1 and 0.5 g litre^?1 respectively. At higher concentrations of these components, there were no further increases in deposition on these latter species. The results were in agreement with those predicted by a mathematical model derived previously, with the exception of the slight decreases in deposition on V.fana and S.alba and smaller increases in deposition than predicted on G.max. The decreases in deposition on the former species were attributed to slight run-off from their easy-to-wet leaves at the higher “Triton X-100” concentrations at the spray volume rate (600 litre ha^?1) used. The poor fit of the observed and predicted spray depositions on G. max was attributed to the nature of its leaves. These are hairy and it is speculated that the fine hairs, rather than the true leaf surface, played a major role in capturing the small spray drops (115-130 μm) created by the laboratory sprayer used in this work. The observed and predicted spray depositions with a set of diluted commercial-type formulations were in good agreement for Setaria viridis (L.) Beauv., Pisum sativum L., Z. mays, with correlation coefficients (r) of 0.985, 0.988 and 0.935 respectively, and also for the more constant depositions on the easy-to-wet species Beta vulgaris L., but slightly less so for Triticum aestivum L. (r = 0.886) in this test. Overall the model was well-behaved, giving a good prediction of the variation in spray deposition on leaves of a range of plant species, provided that these were not extensively hairy, with variation in the dynamic surface tension of the spray solution.     

The effect of the herbicide glyphosate on non‐target spiders: Part II. Indirect effects on Lepthyphantes tenuis in field margins

We have examined the indirect effect of the herbicide glyphosate on the spider Lepthyphantes tenuis in field margins. Glyphosate was applied to a randomised block design field experiment comprising 360, 720 and 1440 g glyphosate AE ha^?1 treatments and an unsprayed control. Spiders were sampled in each month from June to October 1998. Spider abundance was significantly lower in all the treatments than in the unsprayed control. Abundance was also significantly lower in the 720 and 1440 g treatments than in the 360 g treatment. No significant difference could be detected between the 720 and 1440 g treatments. Poisson regression models showed that patterns of decline in L tenuis were related to increasing dead vegetation and decreasing vegetation height. Glyphosate applications only had a within‐season indirect habitat effect on L tenuis as field margins sprayed 16 months after an application of 360 g glyphosate ha^?1 showed no detrimental effect. © 2001 Society of Chemical Industry     

The kinetics of insecticide action. Part I: The properties of a mathematical model describing insect pharmacokinetics

A simple two-compartment model, introducing a parameter (λ) to represent the relative thermodynamic capacities of the compartments, is described for the movement of insecticide from the insect surface (compartment 1) to the region within the insect (compartment 2); loss from compartment 2 is considered. First-order rate constants are assumed for penetration (k_p) and elimination (k_e). The differential equations describing the rates of change of insecticide in each compartment after application of insecticide are solved analytically, and terms describing (a) the integrals of mass of compound in each compartment with time after application, (b) time to a maximum level of insecticide in compartment 2, and (c) distribution and loss of compound from the system with time, are derived. Methods for estimating the three parameters of the model (k_p, k_e and λ) are presented. Further properties of the model with possible toxicological significance have been identified; in particular, the total integral for material in compartment 2 depends only on the elimination rate constant and the applied dose.     

The fungicidal activity of substituted 1, 4-naphthoquinones. Part II: Alkoxy,phenoxy and acyloxy derivatives

A representative group of 1, 4-naphthoquinone derivatives, bearing alkoxy, phenoxy and acyloxy substitutents in the 2-position, has been synthesised and assayed against Botrytis cinerea, Cladosporium fulvum and Venturia inaequalis. The alkoxy compounds exhibited moderate activity, which was enhanced by the presence of a 3-chloro and, to a lesser extent, a 3-bromo substituent. 2-Chloro-3-phenoxy derivatives were highly active, but diphenoxy compounds were inactive. Acyloxy derivatives possessed only weak activity unless a halogen atom was present in the 3-position; benzoyloxy compounds, however, were generally poor fungicides.     

Availability to plants of herbicide residues in soil. Part II: Data for use in vegetable crop rotations

The response of a variety of vegetable crops to fifteen herbicides was estimated in culture solution over concentration ranges chosen to correspond with those that might occur in soil solution. Examples are given to show how these results can be used, in conjunction with the method for estimating the available herbicide residues (in Part I), to decide which crops may safely be sown in soil containing a herbicide residue.     

Surface transport of 2,4-D from small turf plots: observations compared with GLEAMS and PRZM-2 model simulations

A three-year field study was conducted using twelve 7.4×3.7 m plots and simulated rainfall to investigate pesticide run-off following application to a golf course fairway. The plots were sprigged with ‘Tifway 419’ bermudagrass (Cynodon dactylon×C transvaalensis). The dimethylamine salt of 2,4-D [(2,4-dichlorophenoxy)acetic acid] was applied as foliar sprays at a rate of 2.24 kg AI ha⁻¹. Simulated rainfall was applied at an intensity of 29 mm h⁻¹ one day before and 1, 2, 4, and 8 days after the pesticide applications for 0.92, 1.75. 1.75, 0.92, and 0.92 h, respectively. Water run-off was measured using a tipping-bucket apparatus and sub-samples were analyzed for pesticide residues. Data collected from the study were also compared with the GLEAMS and PRZM-2 model simulations for surface water and 2,4-D run-off. Mass and concentration of 2,4-D in run-off decreased rapidly, with 74.5% of the total run-off of 2,4-D occurring in the first run-off event after treatment. When calibrated to the site-specific characteristics, the GLEAMS and the PRZM-2 models adequately simulated the average of surface water run-off over all plots, with normalized root mean square error (NRMSE) and coefficient of determination for linear regression (R²) being 22.8% and 0.917 for GLEAMS, and 23.7% and 0.879 for PRZM-2, respectively. However, both GLEAMS (NRMSE=82.1%, R²=0.776) and PRZM-2 (NRMSE=125.8%, R²=0.513) less accurately simulated 2,4-D concentrations in run-off. © 1999 Society of Chemical Industry     

A simple model of crop loss by weed competition from early observations on relative leaf area of the weeds

A new simple empirical model for early prediction of crop losses by weed competition was introduced. This model relates yield loss to relative leaf area of the weeds shortly after crop emergence using the relative damage coefficient q as the single model parameter. The model is derived from the hyperbolic yield density relationship and therefore accounts for the effects of weed density. It is shown that the model also accounts for the effect of different relative times of weed emergence. A strong advantage of the approach is that it can be used when weeds emerge in separate flushes. The regression model described experimental data on sugar-beet – lambsquarters (Beta vulgaris L. –Chenopodium album L.) and maize-barnyard grass (Zea mays L. –Echinochloa crus-galli L.) competition precisely. The model describes a single relationship between crop yield loss and relative leaf area of the weeds over a wide range of weed densities and relative times of weed emergence. Possibilities for scientific and practical application of the model are discussed.     

The effect of the herbicide glyphosate on non‐target spiders: Part I. Direct effects on Lepthyphantes tenuis under laboratory conditions

We examined the toxic effects of glyphosate to adult female Lepthyphantes tenuis (Araneae, Linyphiidae), a common spider of agricultural habitats. The overspray technique was used to investigate the effect of the herbicide on forty individuals in each of six glyphosate treatments (2160, 1440, 1080, 720, 360 and 180 g ha^?1) and a distilled water control. Spiders collected from the wild were individually placed in exposure chambers and checked every 24 h over a 72‐h experimental period. Mortality of L tenuis remained at less than 10% in all treatments at 24 and 48 h after spray application, and only increased marginally (to 13%) after 72 h. These results support other limited data which suggest that glyphosate is ‘harmless’ to non‐target arthropods. More extended laboratory testing to investigate any side‐effects of glyphosate on the life history of L tenuis and other non‐beneficial invertebrates is required. © 2001 Society of Chemical Industry     

The enantiomeric composition of triadimenol produced during metabolism of triadimefon by fungi. Part II: Differences between fungal species

The fungi Coriolus versicolor, Cladosporium cucumerinum, Botrytis cinerea and Fusarium culmorum, in shake culture, metabolised triadimefon to triadimenol. Analyses by gas–-liquid chromatography of the triadimenol showed that the fungi produced different qualitative and quantitative combinations of the four possible enantiomers, and that these differences were reproducible. The relationship between the enantiomeric composition of the triadimenol produced and the sensitivity of the test fungi to triadimefon, is discussed in the light of published data on the differences in antifungal activity shown by these enantiomers.