Co‐solvent effects on the adsorption of carbofuran by two Indian soils

The adsorption of carbofuran on soils from water‐methanol mixtures has been evaluated by batch shake testing. Two uncontaminated soils having different physicochemical properties were used in these experiments. The volume fraction of methanol in the liquid phase (f_s) was varied from 0.25 to 1.0. Higher adsorption of carbofuran was observed in medium black (silt loam) soil than in alluvial (sandy loam) soil; calculated values of the Freundlich constant (K^m) and distribution coefficient (K_d) showed that adsorption of carbofuran in both soils decreased with increase in f_S values. The decreased carbofuran adsorption in methanol–water mixtures meant a greater potential of ground‐water contamination through leaching from potential sites. The data have been used to evaluate the co‐solvent theory for describing adsorption of carbofuran in methanol–water mixtures. The aqueous phase partition coefficient K_dw (mol g⁻¹) normalized with respect to f_oc and the aqueous phase adsorption constant K_w for carbofuran were evaluated by extrapolating to f_S = 0. © 2000 Society of Chemical Industry     

Determination of carbofuran in pesticide formulations by flow injection spectrophotometry

A flow injection spectrophotometric method for the determination of carbofuran in commercial pesticide formulations was developed. The determination involves on‐line hydrolysis of the extracted carbofuran at room temperature with sodium hydroxide. The resulting carbofuran‐phenol is coupled with diazotized 4‐aminobenzoic acid in order to achieve an appropriate selectivity and sensitivity for the spectrophotometric measurements. The calibration curve is linear over the range 1–10 mg litre⁻¹ of carbofuran. The proposed method has a detection limit of 0.15 mg litre⁻¹ of carbofuran and a sample frequency of 120 injections per hour. The relative standard deviation of six independent determinations of a sample containing 1 mg litre⁻¹ carbofuran was 0.6%. The suitability of the proposed procedure for the determination of carbofuran in commercial pesticide formulations was studied. The procedure provides results comparable to those obtained by liquid chromatographic analysis. © 2000 Society of Chemical Industry     

The physical and chemical properties of the herbicide cinmethylin (SD 95481)

Cinmethylin (SD 95481), is a novel herbicide developed for the selective pre-emergence control of many annual grass weeds in a wide range of temperate and tropical crops. Representing new herbicide chemistry, cinmethylin is in the cineole family. Cinmethylin is a mobile colourless liquid with a boiling point of 313°C under an inert atmosphere at atmospheric pressure. It has a density of 1015 kg m^?3 and a viscosity of 70–90 mPa s, both at 20°C. It is miscible in all proportions with most organic solvents but has a low solubility, 63 mg litre^?1, in water. It has a vapour pressure of 10.2 mPa (20°C) and the vapour pressure/temperature relationship is given by log_e P(Pa)=28.9–9816/T (K). The n-octanol/water partition coefficient is 6850 and soil organic matter/water sorption coefficient (K_om) ranges between 165 and 235 over the three types of soil used in these studies. Cinmethylin is stable in water over the pH range 3–11. Solutions of cinmethylin in water or solvents are reasonably stable to sunlight, though thin films on a quartz surface photooxidise mainly to an ester within 24 h. This rate can be reduced by the addition of photostabilisers or by sorption onto soil surfaces. In an inert atmosphere cinmethylin is stable to high temperatures, though, in air, oxidation occurs at temperatures above 100°C to give the same product as by photodecay.     

Improvement of the desorption of the pesticide 2,4‐D via complexation with HP‐β‐cyclodextrin

Inclusion complex formation of 2,4‐dichlorophenoxyacetic acid (2,4‐D) with hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) has been proposed as a way of modifying the behaviour of the pesticide in the soil environment. The present study assesses the effect of complex formation on 2,4‐D physicochemical properties (aqueous solubility, crystallinity and dissolution rate) and its behaviour on soils. The solid complexes were prepared using different methods (spray drying, kneading and heating in a sealed container). To confirm the complex formation in the solid state differential scanning calorimetry, hot stage microscopy and x‐ray diffraction techniques were employed. Complex formation in solution was studied by phase solubility. The presence of HP‐β‐CD increased the 2,4‐D solubility nine times approximately. The apparent stability constant was determined as 98.6 M ⁻¹. The dissolution rates of the 2,4‐D/HP‐β‐CD complexes were examined and compared with that of the pure pesticide. The results indicated that the complex may have great utility as a rapid way of dissolving the pesticide. Batch experiments were performed to study the adsorption–desorption of 2,4‐D on soils and the influence of the HP‐β‐CD over these processes. The results showed that HP‐β‐CD could increase the desorption of 2,4‐D previously adsorbed on soils. © 2000 Society of Chemical Industry     

Modeling environmental effects on enhanced carbofuran degradation

Prediction of the fate of pesticides in soil is of interest from an environmental (pollution) as well as an agricultural (efficacy, carryover) viewpoint. Two environmental parameters that control microbial degradation of pesticides in soil are moisture and temperature. This study was designed to quantify the impact of soil water content and temperature on microbial degradation rates of the insecticide carbofuran (2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl methyl-carbamate). Carbofuran degradation was determined by monitoring the [ 14 C] carbondioxide production from soils amended with [carbonyl- 14 C]carbofuran. Soils were incubated at seven soil-water tensions over the range of 0–03 to 1–5 MPa, and at five temperatures (10°C to 30°C). The sigmoidal degradation kinetics observed from these incubations were modeled using a general saturation model. For the moisture experiments, maximum rate of hydrolysis and half-life (DT₅₀) were accurately modeled by an exponential relationship. The response of carbofuran degradation to temperature was also well described by an exponential relationship, from which it was estimated that the Q₁₀ associated with the maximum rate was 1.68, and the Q₁₀ for DT₅₀ was 1–89.     

The push–pull strategy for citrus psyllid control

The Asian citrus psyllid (ACP), Diaphorina citri Kuwayama (Hemiptera: Psyllidae), is the only natural vector of Candidatus Liberibacter asiaticus that causes citrus huanglongbing (HLB), a most destructive disease of citrus. Currently, no remedial therapy exists for the disease, and so effective control of ACP is very important in curbing the transmission of the disease. The push–pull strategy should be thoroughly explored as an approach to ACP management. This mini‐review summarises the current progress towards more effective repellent and attractant chemicals through investigating known repellent and attractive plants. Interactions between ACP and its host plants are also addressed, with emphasis on the possible involvement of the host biochemicals in attracting the insect. Potential ways to increase the effectiveness of the pull–push strategy are briefly discussed. It is expected that the pull–push strategy will be gradually developed following more extensive research. © 2014 Society of Chemical Industry     

The effect of initial concentration of carbofuran on the development and stability of its enhanced biodegradation in top‐soil and sub‐soil

Carbofuran was incubated in top‐soil and sub‐soil samples from a pesticide‐free site at a range of initial concentrations from 0.1 to 10 mg kg⁻¹. Amounts of the incubated soils were removed at intervals over the subsequent 12 months, and the rate of degradation of a second carbofuran dose at 10 mg kg⁻¹ was assessed. An applied concentration as low as 0.1 mg kg⁻¹ to top‐soil resulted in more rapid degradation of the fresh addition of carbofuran for at least 12 months. The degree of enhancement was generally more pronounced with the higher initial concentrations. When the same study was conducted in sub‐soil samples from the same site, an initial dose of carbofuran at 0.1 mg kg⁻¹ resulted in only small increases in rates of degradation of a second carbofuran dose. However, degradation rates in the sub‐soil samples were, in many instances, considerably greater than in the corresponding top‐soil samples, irrespective of pre‐treatment concentration or pre‐incubation period. Initial doses of 0.5 mg kg⁻¹ and higher applied to sub‐soil successfully activated the sub‐soil microflora. Application of the VARLEACH model to simulate carbofuran movement through the soil profile indicated that approximately 0.01 mg kg⁻¹ of carbofuran may reach a depth of 70 cm 400 days after a standard field application. The results therefore imply that adaptation of the sub‐soil microflora (c 1 m depth) by normal field rate applications of carbofuran is unlikely to occur. In experiments to investigate this in soils exposed to carbofuran in the field, there was no apparent relationship between top‐soil exposure and degradation rates in the corresponding sub‐soils. The results further confirmed that some sub‐soil samples have an inherent capacity for rapid biodegradation of carbofuran. The high levels of variability observed between replicates in some of the sub‐soil samples were attributed to the uneven distribution of a low population of carbofuran‐degrading micro‐organisms in sub‐surface soil. There was no apparent relationship between soil microbial biomass and degradation rates within or between top‐soil and sub‐soil samples. © 2001 Society of Chemical Industry     

Structure–Activity Relationships of Herbicidal Aryltriazolinones

A series of substituted aryltriazolinones, known to inhibit protoporphyrinogen oxidase, were prepared and their structure–activity requirements at positions 4 and 5 of the aromatic ring investigated. A QSAR equation obtained for substituents at the 5 position identified the hydrophobicity term π and the Sterimol minimum width B₁ as the two parameters affecting in-vitro biological activity. Greenhouse pre-emergence activity correlated with in-vitro activity and the hydrophobicity term π of the substituent at that position. It was found that the phenoxy-4-oxyacetate group at aromatic position 5 was an outlier and had to be considered separately. SAR analysis of substituents at aromatic position 4 revealed that two different models were required to explain all observed substituent effects. In the first model, where the 5 position was occupied by hydrogen, the 4-chlorobenzyloxy group at aromatic position 4 gave the best compound. The second model, where the 5 position of the aromatic ring was occupied by a group other than hydrogen, resulted in a QSAR equation, previously derived, which links substituent effects at position 4 with π and with the electronic para inductive term F_p. In this model the chloro group provides optimum biological activity. The need to separate the aryltriazolinone herbicides into several different classes in order to explain their substituent effects at aromatic positions 4 and 5 could be rationalized if more than one binding conformation, within the same binding site, is possible. © 1997 SCI     

Cinétique de dissolution dans l'eau de l'atrazine, de la propazine et de la simazine

The kinetics of dissolution of atrazine, propazine and simazine in water The solubaility and kinetics of solubilization of atrazine, propazine and simazine in water were studied at different temperatures. The apparent order of the dissolution reactions is 1 for atrazine and propazine and 2 for simazine. The solubility and rate constants are Increasing functions of the temperature. Activation energies of solubilization are of the order of 41 to 4–8 kcal/mole; they correspond to a 30% decrease in the time of a 50% solubilization when temperature increases by 10°C. It seems therefore that the effectiveness of a treatment can depend in part on the amount of rain and the soil temperature.     

Synthetic pyrethroids containing a C–C triple bond

The three commercial synthetic pyrethroids containing a carbon–carbon triple bond, α-ethynyl-2-methylpent-2-enyl (1R)-trans-chrysanthemate, (S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl (1R)-trans,cis-chrysanthemate and [2,5-dioxo-3-(2-propynyl)-1-imidazolidinyl]methyl (1R)-trans-chrysanthemate are reviewed with emphasis on their inventive histories. Their chemistry and efficacy are described briefly. The relationship between stereochemistry and the biological activity is also discussed. © 1998 SCI.     

Influence of adsorption–desorption phenomena on pesticide run-off from soil using simulated rainfall

The surface run-off of a number of pesticides (diuron, isoproturon, atrazine, alachlor, aclonifen, trifluralin, lindane and simazine), chosen for their range of adsorption behaviours, was studied using simulated rainfall applied to small plots over a short time (one hour). Pesticides were applied together onto bare soil using two different sandy loam soils from Jaillière and Coet Dan sites. The surface run-off samples were collected throughout the running of the event and concentrations of pesticides were measured in both liquid and solid phases. Sorption isotherms for isoproturon and diuron on Jaillière soil as well as eroded particles were measured under equilibrium conditions and compared to their partitioning during surface run-off. At the rainfall intensity used, both soils generated a large load of eroded particles. The average run-off flow rate increased with time for the Jalliére soil, while it remained relatively constant at a higher level for the Coet Dan soil. The concentrations of each pesticide in the run-off samples decreased as the experiments proceeded. The pesticides were classified into two types by their partitioning between the solid and liquid phases. Atrazine, simazine, diuron, isoproturon and alachlor were mainly transported in surface run-off water. By contrast, 90% of trifluralin and aclonifen was adsorbed onto eroded particles. Lindane was intermediate, with a 37% adsorption level. When the contribution of eroded particles was minor, the agrochemical concentrations were inversely proportional to the water flow rate. We have proposed a model that describes the mass of chemicals extracted from soil into surface water during a surface run-off event of a given average duration and flow rate. This model takes into account the dilution of the soil solution and the desorption of chemicals through two parameters called, respectively, the dilution factor and the extraction retardation factor. The desorption kinetic was the limiting step in the surface run-off of weakly sorbed chemicals, such as isoproturon. © 1999 Society of Chemical Industry     

Rate of volatilisation of pesticides from soil surfaces; comparison of calculated results with those determined in a laboratory model system

A laboratory model system for the determination of the volatility of non-ionic pesticides from soil surfaces is presented. The pesticides examined were the insecticides methidathion, diazinon, and isazophos, the herbicide metolachlor, and the fungicide metalaxyl. The rates of volatilisation of these compounds from soil increased with increasing pesticide concentration, temperature and air flow rate and with decreasing soil organic matter content. The volatilities of the same pesticides were also calculated by using their vapour pressure, water solubility and soil adsorption data. The excellent correlation between calculated and experimental results showed that information on the volatility of a chemical can be obtained simply by calculation. Such calculations allow the classification of each pesticide according to its volatility, and therefore represent a useful alternative for volatility studies in laboratory model systems.     

Non‐target‐site mechanism of glyphosate resistance in Italian ryegrass (Lolium multiflorum)

In Shizuoka Prefecture, Japan, glyphosate‐resistant Lolium multiflorum is a serious problem on the levees of rice paddies and in wheat fields. The mechanism of resistance of this biotype was analyzed. Based on LD₅₀, the resistant population was 2.8–5.0 times more resistant to glyphosate than the susceptible population. The 5‐enolpyruvyl‐shikimate‐3‐phosphate synthase (EPSPS) gene sequence of the resistant biotype did not show a non‐synonymous substitution at Pro106, and amplification of the gene was not observed in the resistant biotype. The metabolism and translocation of glyphosate were examined 4 days after application through the direct detection of glyphosate and its metabolite aminomethylphosphonic acid (AMPA) using liquid chromatograph‐tandem mass spectrometer (LC‐MS/MS). AMPA was not detected in either biotype in glyphosate‐treated leaves or the other plant parts. The respective absorption rates of the susceptible and resistant biotypes were 37.90 ± 3.63% and 41.09 ± 3.36%, respectively, which were not significantly different. The resistant biotype retained more glyphosate in a glyphosate‐treated leaf (91.36 ± 1.56% of absorbed glyphosate) and less in the untreated parts of shoots (5.90 ± 1.17%) and roots (2.76 ± 0.44%) compared with the susceptible biotype, 79.58 ± 3.73%, 15.77 ± 3.06% and 4.65 ± 0.89%, respectively. The results indicate that the resistance mechanism is neither the acquisition of a metabolic system nor limiting the absorption of glyphosate but limited translocation of the herbicide in the resistant biotype of L. multiflorum in Shizuoka Prefecture.     

Adsorption–desorption of 2,4-D by hydroxy aluminium montmorillonite complexes

Adsorption–desorption characteristics of 2,4-dichlorophenoxyacetic acid (2,4-D) on pure montmorillonite and synthetic chlorite-like complexes [Al(OH)_x-montmorillonite complexes, obtained by coating montmorillonite surfaces with different amounts of Al(OH)_x] were investigated. The equilibrium adsorption of 2,4-D was described by both Langmuir and Freundlich type isotherms. The extent of adsorption as well as the type of interaction between adsorbate and adsorbent was affected by the nature of incubation buffer and the charge characteristics of supports. At pH 5·6 and in acetate buffer, 2,4-D was negatively adsorbed by montmorillonite and herbicide adsorption capacity increased with increasing amounts of Al(OH)_x species loaded on montmorillonite surfaces. When adsorption experiments were performed at the same pH but in phosphate buffer, strong reductions of both the amount of adsorbed pesticide and its affinity for the adsorbents were measured. Evidently, phosphate anions competed strongly with 2,4-D anions for the sorption site on chlorite-like complexes. Furthermore, desorption tests revealed that a large amount (about 60%) of the pesticide was firmly bound to the clay and was not removed even after repeated washings or 24 h exposure to desorption solution. Both electrostatic interactions between the negative COO^- moieties of 2,4-D and the positive sites on clays, and ligand exchanges of COO^- groups with -OH or water at the clay surface were probably involved in the adsorption process. ©1997 SCI     

Dimethoxypyrimidines as novel herbicides. Part 4. Quantitative structure–activity relationships of dimethoxypyrimidinyl(thio)salicylic acids

The activity of a number of O-(4,6-dimethoxypyrimidin-2-yl)salicylic acids and their thio analogs inhibiting acetolactate synthase (ALS) preparation was measured. The effects of substituents on the salicylic-benzene ring on the inhibitory activity were analyzed quantitatively with physicochemical substituent parameters. For 6-substituted (thio)salicylic acids, the activity was shown to vary parabolically with the ‘intramolecular’ steric parameter ( E_s ). In addition, the higher steric dimension of substituents in terms of the STERIMOL width or length parameter lowered the activity. The field-inductive electron-withdrawing property of the 6-substituents in terms of the Swain–Lupton–Hansch F was favorable for the activity of salicylic acid series. In 5-substituted salicylic acids, the activity was increased by electron-donating substituents with smaller size. The relationships between ALS inhibitory and herbicidal activities were also analyzed with some weed species. Both pre- and post-emergence activities against barnyard grass, Echinochloa crus-galli, were linearly related to the ALS inhibitory activity after allowing for the hydrophobic factor that may contribute to the transport processes. Those against two broad-leaved weed species, Polygonum convolvulus and Abutilon theophrasti were linearly related to the in-vitro activity with no significant participation of the hydrophobic factor. © 1998 SCI     

Residues of the herbicide fenoxaprop‐P‐ethyl,its agronomic safener isoxadifen‐ethyl and their metabolites in rice after field application

BACKGROUND: Fenoxaprop‐P‐ethyl is a herbicide used on cereals and in particular on rice, the degradation of which leads to several relevant metabolites. The herbicide is used together with an agronomic safener such as isoxadifen‐ethyl, which also generates some metabolites. The present work was aimed at developing and validating an analytical method for the determination of the above parent compounds and their main metabolites in the edible fractions of rice. Parent compounds were extracted in acetonitrile and determined by gas chromatography with a mass spectrometer detector, while metabolites were extracted in acetonitrile and analysed by liquid chromatography tandem mass spectrometry. RESULTS: The method was validated through recovery tests in rice straw, grain and plant: accuracy was in the range 76–86% and 90–103% for parent compounds and metabolites respectively. Precision, as relative standard deviation, was in the range 3–11% and 6–17% for parent compounds and metabolites respectively. The limit of detection was 0.01 mg kg^?1 for each analyte, while the limit of quantification was set at 0.05 mg kg^?1. CONCLUSION: The analytical method is suitable for quantitative determination of each analyte considered in rice commodities. Copyright © 2010 Society of Chemical Industry     

Synthesis and Structure–Activity Relationships of Miticidal 4,5-Dihydropyrazole-5-thiones

A series of novel 4,5-dihydropyrazole-5-thiones (DHPs) was synthesised by treating the corresponding dihydropyrazolones with ‘Lawesson’s reagent and evaluated for miticidal activity against two-spotted spider mites (Tetranychus urticae Koch). Of these, 3-(4-chlorophenyl)-4,4-dimethyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-4-ethyl-4-methyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-1-phenyl-4,5-dihydropyrazole-5-thione-4-spirocyclopentane and 4,4-dimethyl-1-phenyl-3-(4-trifluoromethyl-phenyl)-4,5-dihydropyrazole-5-thione were highly active (pEC₅₀>4·0) and were more effective than the miticide dicofol (pEC₅₀=3·879), which has traditionally been used for the control of phytophagous mites. Structure–activity relationship (SAR) studies were performed on each position of the pyrazole ring of DHPs. The results indicated that the unsubstituted phenyl, 4-substituted phenyl and thioxo groups on the 1-, 3- and 5-positions of DHPs respectively were required for activity. Quantitative SAR studies using physicochemical parameters of substituents and the capacity factor k′ as a hydrophobicity index suggested that: (a) the activities of all types of DHPs examined were mainly dominated by hydrophobicity, (b) the bulkiness of 4-substituents of the 3-phenyl ring favoured the activity and (c) the log k′ optimum for all DHPs was 1·675, equivalent to a log P_ow value of c. 5·0.     

A method for determining the volatility of active ingredients used in plant protection

The paper describes a gravimetric method of determining the volatility (evaporation rate) of pesticides. The measuring apparatus may be set at any temperature between ～15 and 80°C; the dry air flowing through the apparatus is regulated by valves between -0.2 1/h and 300 1/h. Figures available for vapour pressure reveal a mathematical relation between vapour pressure and evaporation rate. This can be used as a simple method of determining the vapour pressure of any substance at 20°C by determining the evaporation rate when the air current is flowing at 50 l/h. The effects of the temperature and the air flow rate on the evaporation rate are also analysed.     

Effect of heat-treating soil and straw on the subsequent adsorption of chlortoluron and atrazine

The adsorption of chlortoluron and atrazine was measured on a range wheat straw residues that had been heated for periods of 1–5 min at temperatures up to 700°C and and on three soils that had been heated at up to 250°C for 1–5 min. Adsorption of both compounds by straw ash increased with increasing temperature of pretreatment. Atrazine adsorption by any of the soils was not changed markedly chlortoluron absorption was increased with two of the three soils. The results are discussed in terms of the changes in organic functional groups, that are likely to have been produced by the treatment, in relation to the adsorption mechanisms thatmay operate on the two compounds. Adsorption of chlortoluron by mixtures of ash and soil was less than the sum of the adsorption capacities of each component on its own in the cases of two out of three soils. It is concluded that the effect of straw burning on herbicide performance in the field will be variable but could be substantial. Le chauffage du sol et du chaume: influence sur l’adsorption ultérieure de chlortoluron et de l'atrazine