Spectrophotometric determination of ziram and zineb using 4-(2-pyridylazo) resorcinol

A spectrophotometric method has been developed for the determination of ziram (zinc bis(dimethyldithiocarbamate)) and zineb (zinc ethylenebisdithiocarbarnate) by converting these into a zinc-4-(2-pyridylazo)resorcinol complex, which is dissolved in acetone and water and the absorbance measured at 490 nm against a reagent blank. Beer's law is obeyed over the concentration ranges 0.025-1.25 and 0.025-1.5 mg litre^?1 for ziram and zineb respectively in the final solution. The method is sensitive and can be used for the direct determination of ziram and zineb in commercial formulations, grains (rice and wheat) and synthetic mixtures (in the presence of various other dithiocarbamates). The limit of determination of ziram and zineb from foodstuffs in 0.2 mg kg ^?1.     

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     

Gas-liquid chromatographic determination of hydrazine in maleic hydrazide formulations and in samples stored at an elevated temperature

A method is described for the analysis of small amounts of hydrazine in maleic hydrazide formulations. Following derivative formation with pentafluorobenz-aldehyde, the pentafluorobenzaldehyde azine was extracted with hexane and determined by gas-liquid chromatography with electron-capture detection. Recoveries of 72-80% were obtained from samples fortified with 1 and 10 μg of hydrazine. The limit of detection was 0.05 mg kg^?1. Fourteen commercial formulations with maleic hydrazide concentrations ranging from 180-360 g litre^?1 were investigated. The hydrazine content of the maleic hydrazide used in these formulations ranged from less than 0.05 to 53 mg kg^?1. During the storage of two samples at 50°C for 10 weeks, the hydrazine contents increased from 2.2 to 124 and 0.4 to 54 mg litre^?1, respectively.     

Susceptibility pattern and development of resistance in the diamondback moth,Plutella xylostella L,to Bacillus thuringiensis Berl var kurstaki in India

Base‐line susceptibility for six‐day‐old larvae of the diamondback moth, Plutella xylostella, against Bacillus thuringiensis var kurstaki (Biobit^®) was studied by a cabbage leaf disc dip bioassay technique. Diamondback moth from 13 locations in seven different states spread over a distance of about 3000 km longitudinally was used for these studies. Forty‐eight‐hour LC₅₀ values varied from 1.0 to 10.97 mg AI litre⁻¹. Further investigations on the development of resistance under laboratory conditions showed an increase in LC₅₀ from 2.76 (for unselected F₁ generation) to 5.28 mg AI litre⁻¹ (for selected F₉ generation), using a selection concentration of 6.4 mg AI litre⁻¹. This suggested a possibility of the development of resistance under field conditions if there were to be extensive and indiscriminate use of B thuringiensis. These findings are discussed in relation to integrated pest management and the mechanisms of resistance in resistance management tactics. © 2000 Society of Chemical Industry     

A rapid bioassay for the detection of photosynthesis inhibitors in water

A modified leaf disc buoyancy procedure for the detection of photosynthesis-inhibiting residues in water is described. The modifications proposed, mainly the presence of sodium hydrogen carbonate in the infiltration solution, increased the sensitivity of the method and reduced the time required. The substituted urea and 1,3,5-triazine herbicides diuron, linuron, monuron, atrazine, ametryn and atraton were detected below 0.7 mg litre^?1 using cucumber (Cucumis sativus L., cv. ‘Dalia’) leaf discs. A concentration as low as 0.09 mg diuron litre^?1 could be detected. Although bean (Phaseolus vulgaris L., cv. ‘Bulgarian’) leaf tissue was less sensitive in this bioassay than cucumber, 0.3 mg diuron litre^?1 could still be detected. The test, being very rapid (less than 30 min per determination) and relatively sensitive, could be used for the detection of photosynthesis inhibitors in recycled water used for irrigation.     

Insecticidal activity of surfactants and oils against silverleaf whitefly (Bemisia argentifolii) nymphs (Homoptera: Aleyrodidae) on collards and tomato

The insecticidal activities of four surfactants (Cide‐kick, Silwet L‐77, M‐Pede and APSA‐80), a dishwashing detergent (New Day), a mineral oil (Sunspray oil), a cotton seed oil and a vegetable oil, alone or in combination, were tested against nymphs of Bemisia argentifolii Bellows & Perring on collards and tomato. Silwet L‐77 was more effective (>95% mortality) than Cide‐Kick or APSA‐80 at rates from 0.25–1.00 g AI litre⁻¹ but caused severe phytotoxicity to tender tomato leaves at all but the lowest rate. New Day dish detergent at 2.0 ml litre⁻¹ caused mortality (95%) comparable to M‐Pede insecticide soap at 10‐fold greater concentration. A New Day ingredient, cocamide DEA, was considerably more active than the other ingredients or the commercial mixture. Additional surfactants added to Sunspray oil increased efficacy in some treatments, but not others. Toxic responses of 2nd‐ and 3rd‐ instar whiteflies to vegetable oil and cotton seed oil at 5.0 and 10.0 ml litre⁻¹ plus 0.4 g AI litre⁻¹ APSA‐80 ranged from 22.1 to 79.9% and 66.3–88.7% mortality, respectively. Whitefly mortality was greater on tomato than on collard in six of seven instances when differences between host plants were significant. Our results indicate that the these surfactants and oils have good potential for controlling B argentifolii. © 2000 Society of Chemical Industry     

Carbofuran-induced biochemical changes in Clarias batrachus

The effect of carbofuran, an organo-carbamate pesticide, upon the level of protein as well as the activity of lactate dehydrogenase (EC 1.1.1.28, LDH) was studied by exposing the teleost fish, Clarias batrachus, to different subacute con-centrations (0·01 and 0·02 mg litre^-1) for 96 h and 15 days. The results showed a drastic decrease in the protein content in different body organs of the fish. The pesticide also caused a significant decrease in the level of activity of LDH in different body tissues of the fish, the effect being more pronounced in the gills, muscle, brain and liver than in kidney and heart. The decrease in protein content and the activity of LDH in fish tissues was more marked at the higher concentration of the pesticide for the longer duration of treatment. The results suggested that carbofuran has an effect at very low concentration (compared to its LC₅₀ value) possibly at the level of protein metabolism, and also inhibits the activity of LDH, the terminal glycolytic enzyme. © 1998 SCI     

Disappearance of carbosulfan residues in peaches

The disappearance kinetics of the carbamate insecticide, carbosulfan, applied at 2 kg AI ha^?1 (‘Marshal’ 250 g litre^?1 EC) in peaches was studied. Degradation took place in two consecutive stages (0–28 and 28–57 days), with half-lives of 7.4 and 17.5 days, respectively. The residues obtained 57 days after treatment did not exceed 0.2 mg kg^?1. When treatments were carried out 30, 21 and 14 days before the probable date of harvest (date of fruit maturation) with two doses (1.0 and 2.0 g formulated product litre^?1) and two volumes applied (750 and 1500 litre ha^?1), the residual levels detected were between 0.122 mg kg^?1 (30 days before harvest) and 0.4 mg kg^?1 (14 days before harvest). The major metabolite, carbofuran, was never detected above its determination limit of 0.004 mg kg^?1 throughout the whole study.     

Spectrophotometric determination of ferric dimethyldithiocarbamate (ferbam) in formulations,grain and apples using 1, 10-phenanthroline

A procedure has been developed for the determination of ferbam (ferric dimethyldithiocarbamate) by converting it into ferbam-phenanthroline complex, which is dissolved in acetone + water (1 + 1 by volume), and the absorbance measured at 490 nm against a reagent blank. Beer's law is obeyed over the concentration range 0–8–20-0 mg litre^?1 in the final solution. The method is sensitive, selective and can be used for the direct determination of ferbam in commercial samples, in mixtures with various other dithiocarbamates (ziram, zineb, maneb, etc.) and from grains (rice and wheat) and apples. The limit of determination from foodstuffs is 0–4 mg kg^?1.     

Effect of Hydrogen Cyanide and Carbonyl Sulphide on the Germination and Plumule Vigour of Wheat

Several factors which may influence the germination of wheat fumigated with hydrogen cyanide or carbonyl sulphide were investigated. Dosages of hydrogen cyanide ranged from 10 mg litre⁻¹ for 24-h exposure up to 150 mg litre⁻¹ for 96-h exposure. Dosages of carbonyl sulphide ranged from 25 mg litre⁻¹ for 24-h exposure up to 500 mg litre⁻¹ for 72-h exposure. The experiments were conducted on wheat of 11·4, 13·8 and 15·7% moisture content. The higher levels of these fumigants exceed those needed for control of insects in wheat. Germination was not diminished and may have been slightly enhanced with hydrogen cyanide, but was diminished by high levels of carbonyl sulphide in the drier wheat. The plumule length was reduced following all dosages of hydrogen cyanide, but only after high dosages of carbonyl sulphide, especially on the driest wheat. It is concluded that hydrogen cyanide and carbonyl sulphide could be used to control insects in wheat without affecting seed viability, provided that concentrations are carefully controlled.     

Laboratory Evaluation of the Novel Naturally Derived Compound Spinosad against Ceratitiscapitata

Laboratory studies were conducted to determine the effect of the naturally derived compound spinosad on Ceratitis capitata Wied. (Diptera, Tephritidae). The organophosphate fenthion was used as a standard. Direct dose-dependent mortality and reduced fecundity were observed in oral treatment of adults with spinosad. The LC₉₀ values 14 h and seven days after treatment were 19·50 and 0·49 mg litre⁻¹ respectively. Fenthion was less active (the LC₅₀ eight days after treatment was 1·17 mg litre⁻¹) and did not affect the fecundity of the fly. Adults were also very susceptible to spinosad and fenthion via residual contact. For spinosad, 100% mortality was recorded 48 h after treatment for a dose of 10 mg litre⁻¹. Spinosad was more effective than fenthion in suppressing larval development when neonate larvae were reared on treated diet supplemented with a range of concentrations from 0·02 to 0·83 mg kg⁻¹ diet. Last-instar larvae were much less susceptible to spinosad or fenthion when exposed via dipping or when they pupated in treated medium and both products had similar performance. A lack of ovicidal activity was observed in direct egg-treatments with spinosad but significant reductions from 1 mg litre⁻¹ onwards were recorded for fenthion.     

Efficacy of Surface Dust Treatments of Pirimiphos-Methyl and Etrimfos when Applied to Commercially Stored Wheat and Barley

Commercially stored wheat and barley were surface treated with dust formulations of pirimiphos-methyl and etrimfos at the manufacturer's recommended application rate. Samples were taken at four-weekly intervals for 32 and 16 weeks for wheat and barley respectively. Pesticide efficacy was determined using insect bioassays and chemical analysis of residues. There was no evidence to suggest a decline in residue levels of either pesticide over the experimental period. However, considerable variation was observed in the residue levels recorded at different sample points and also between residue levels recorded for the same point over the trial period. Control of susceptible strains of Tribolium castaneum (Herbst), Oryzaephilus surinamensis (L.) and Sitophilus granarius (L.) was achieved where recovered pesticide residues remained above 1 mg kg⁻¹ pirimiphos-methyl and 1·6 mg kg⁻¹ etrimfos.     

Pesticidal properties of parthenin (from Parthenium hysterophorus) and related compounds

Eleven sesquiterpene lactone derivatives of parthenin ( 1 ), obtained from wild feverfew, Parthenium hysterophorus, were prepared by chemical and photochemical transformations. The compounds tested were a pyrazoline adduct ( 2 ) of parthenin, its cyclopropyl ( 3 ) and propenyl ( 4 ) derivatives, anhydroparthenin ( 5 ), a dihydro‐deoxygenated product ( 6 ), a formate ( 7 ) and its corresponding alcohol ( 8 ) and acetate ( 9 ), a rearranged product ( 10 ), lactone ( 11 ) and hemiacetal ( 12 ). All these derivatives, along with parthenin, were tried for their antifeedant action against sixth‐instar larvae of Spodoptera litura, for insecticidal activity against the adults of store grain pest Callosobruchus maculatus, for phytotoxic activity against Cassia tora, and for nematicidal activity against the juvenile stage‐II (J₂) of the root knot nematode Meloidogyne incognita. Antifeedent bioassay revealed that parthenin is moderately antifeedant. Among the derivatives, the saturated lactone ( 11 ) was found to be about 2.25 times more active than parthenin. The pyrazoline adduct ( 2 ) was found to be the most effective as an insecticide, with LC₅₀ values after 24, 48 and 72 h of 96, 43 and 32 mg litre⁻¹, respectively, which are comparable with neem extract. Compound 4 was found to be the most effective inhibitor of germination and seedling growth of C tora, with ID₅₀ values for germination, plumule length and radicle length of 136, 326 and 172 compared with 364, 738 and 427 mg litre⁻¹, respectively, for parthenin. Compound 10 was found to be the most effective in terms of nematicidal activity. The LC₅₀ values for this compound were 273 and 104 mg litre⁻¹, respectively, after 48 and 72 h compared with 862 and 512 mg litre⁻¹ observed for parthenin after 48 and 72 h. © 2001 Society of Chemical Industry     

Laboratory and field evaluation of spinosad against the gypsy moth,Lymantria dispar

The toxicity of the naturally derived insecticide spinosad was tested against the gypsy moth, Lymantria dispar. Bioassays using red oak leaf disks, treated with spinosad in a Potter spray tower, yielded an LC₅₀ value of 0.0015 µg AI cm⁻² (3‐day exposure; 13‐day evaluation; 2nd instar larvae). Applied to foliage to run‐off in the laboratory (potted red oak seedlings) and the field (4 m‐tall birch trees), spinosad effectively controlled 2nd instar larvae at concentrations ranging from 3 to 50 mg litre⁻¹. Toxicity in the laboratory, and efficacy and persistence in the field, were comparable to those achieved with the insecticide permethrin. Laboratory studies supported field observations that control was achieved in part by knockdown due to paralysis. In addition, laboratory results demonstrated that crawling contact activity may play an important role in field efficacy; 50% of treated larvae were paralyzed 16 h after a 2‐min crawling exposure to glass coated with a 4 mg litre⁻¹ spinosad solution. © 2000 Society of Chemical Industry     

Effect of fipronil seed treatments on the germination and early growth of rice

Fipronil seed treatments were evaluated to determine whether they directly influence germination and subsequent seedling growth in rice (Oryza sativa L). Continuous seed exposure to fipronil (four days) at 2 000 mg litre⁻¹ significantly impaired germination (P < 0.001). When exposure was restricted to a 1-h period 48 h after the initiation of germination, early post-germination growth was also impaired (assessment two days after exposure, P < 0.05). The proportion of seeds satisfying our criteria for normal germination fell by 2.3 and 2.6% respectively across 17 cultivars. Cultivar effects were highly significant (P < 0.001). When exposure to fipronil (2 000 mg litre⁻¹) was restricted to 2 h at initial seed wetting no significant growth impairment occurred. No significant differences (P > 0.05) were found between shoot lengths or root system dry weights of control plants and plants developing from seed exposed continuously (two days) to fipronil at rates of up to 2 000 mg litre⁻¹ during germination and harvested nine days after sowing. Treating germinated seed with fipronil for 1 h immediately prior to sowing at rates of up to 4 000 mg litre⁻¹ did not result in significant changes (P < 0.05) in plant growth parameters at either nine or 25 days after sowing. No evidence of fipronil having a direct phytostimulatory effect on rice was obtained. © 1999 Society of Chemical Industry     

In-vitro and in-vivo nematicidal activities of the cyclic dodecapeptide omphalotin A

Omphalotin A, a cyclic dodecapeptide produced by submerged cultures of the basidiomycete Omphalotus olearius, exhibited in-vitro and in-vivo nematicidal activity. Meloidogyne incognita was the most sensitive nematode. At 2.0 mg litre⁻¹, 50% of the nematodes were dead after one hour. Heterodera schachtii, Radopholus similis and Pratylenchus penetrans were affected at higher concentrations. Incorporated into agar, the compound prevented infection of cucumber seedlings by M. incognita at concentrations of 1 mg litre⁻¹ and higher. In glasshouse tests, complete protection of cucumbers and lettuce was achieved between 2.5 and 10 mg litre⁻¹. No insecticidal activity was observed when Plutella xylostella, Phaedon cochleariae or Spodoptera frugiperda were fed material containing 4 g kg⁻¹ of omphalotin A. © 1999 Society of Chemical Industry     

Changes induced by phorate in the carbohydrate metabolism of the snail Lymnaea acuminata

Carbohydrate metabolism was studied in the hepatopancreas, mantle, intestine and foot of the snail Lymnaea acuminata, exposed to 40% and 80% of the LC₅₀ dose of phorate (12 and 24 mg litre^?1, respectively) for 24 and 48 h. Following treatment with the pesticide, the rate of oxygen consumption and the glycogen contents were reduced, while the levels of lactic acid and reducing sugars were enhanced. Withdrawal of the pesticide for 7 days after exposure of the snails to 12 mg of phorate litre^?1 for 48 h did not reverse these changes.     

气相色谱-质谱联用检测农药制剂中8种有机溶剂类助剂的含量及市场样品筛查

建立了农药制剂中甲醇、甲苯、乙苯、邻二甲苯、对二甲苯、间二甲苯、N,N-二甲基甲酰胺 (DMF) 和二甲基亚砜 (DMSO) 8种有机溶剂类助剂的气相色谱-质谱联用 (GC-MS) 测定方法,并运用该方法对市售的206种液体农药制剂进行了检测,获得市售农药制剂中目标助剂的含量。农药制剂经乙腈稀释10 000倍后,在选择离子监测 (SIM) 模式下测定,8种助剂的质量浓度与对应的峰面积间线性相关性良好,r为0.999 2~0.999 8;8种助剂在100~1 000 mg/kg添加水平下,回收率为76%~116%,相对标准偏差 (RSD) 均小于17%;8种助剂的定量限 (LOQ) 在100~500 mg/kg之间。对206种市售液体农药制剂的筛查结果表明:8种助剂的检出率在0.5%~31.1%之间,超标率在7.2%~14.5%之间,液体农药制剂中苯类溶剂使用量较高。该方法可为农药加工、管理和助剂限量标准制定提供依据,农药制剂中有毒溶剂的使用应引起生产企业和农药管理部门的重视。     

Sensitivity of European Plasmopara viticola populations to cymoxanil

Between 1995 and 1997, 278 grape downy mildew (Plasmopara viticola) populations originating from European vineyards were characterised for their sensitivity to cymoxanil in a leaf-disc assay. The sensitivity profile revealed a wide distribution, with minimum inhibitory concentrations (MIC) ranging from 10 to more than 800 mg litre⁻¹. EC₅₀ values ranged from 1 to more than 800 mg litre⁻¹ with an average of 125 mg litre⁻¹. The sensitivity distribution was stable between 1995 and 1997. Surprisingly, populations from Portugal appeared significantly more sensitive than those from France or Italy, which could not be linked to differential cymoxanil usage in these countries. P viticola populations collected outside Europe and never exposed to cymoxanil appeared significantly more sensitive than exposed European populations, with an average EC₅₀ value of 10 mg litre⁻¹. The level of sensitivity of European P viticola populations was relatively unaffected by the number of cymoxanil applications made during a season or by the number of years of cymoxanil use. No link was found between the level of sensitivity in the leaf-disc assay and the level of performance of the cymoxanil mixtures used in the fields where the populations originated. Specific field trials conducted in Italy and Portugal have shown that the performance of cymoxanil-based mixtures remained good even on populations of the grape downy mildew fungus characterised as less sensitive in the leaf-disc assay. While there are no baseline sensitivity data for pre-commercialisation P viticola populations, the results of our study suggest that a shift in sensitivity (12.5-fold) may have occurred in some areas since introduction of cymoxanil on grapes nearly 20 years ago. Because cymoxanil is never used alone, it is difficult to determine whether or not practical resistance is occurring in European vineyards. © 1999 Society of Chemical Industry     

Biodegradation of the Organophosphate Insecticide Coumaphos in Highly Contaminated Soils and in Liquid Wastes

Approximately 400000 litres of cattle dip wastes containing approximately 1500 mg litre⁻¹ of the organophosphate insecticide coumaphos are generated yearly along the Mexican border from a USDA program designed to control disease-carrying cattle ticks. Use of unlined evaporation pits for the disposal of these wastes has resulted in highly contaminated soils underlying these sites. Previous work has shown that microbial consortia present in selected dip wastes can be induced to mineralize coumaphos. Our results demonstrate that similar microbial consortia are present in coumaphos-contaminated soils from eight waste sites and that these organisms are capable of mineralizing cou-maphos in these soils using soil slurries to less than 1 mg litre⁻¹ in 7–10 days at 28°C. In addition, our results show that these consortia are able to colonize pea gravel in trickling gravel filters and can be used in these filters to metabolize coumaphos from dip wastes to less than 0·1 mg litre⁻¹ in 7–10 days at 28°C. These simple systems offer potential low cost means to detoxify coumaphos-containing wastes and to bioremediate soils contaminated with this organophosphate compound.