A field unit for determining dimethoate in fruit and vegetable dips

The concentration of dimethoate in post-harvest dips needs to be maintained at 400 or 500 mg litre^?1 to ensure that fruit fly are killed and also to keep residue levels below the MRL. A field unit which contains a colorimeter, a heating block and cooling positions has been evaluated. The diluted dip sample produces a colour with 4-(p-nitrobenzyl)pyridine after heating and the addition of tetraethylenepentamine. Precision of the unit was acceptable for a field test (repeatability of ± 10.1%) and there was reasonable agreement between determinations made on the unit and by an HPLC method for a range of dimethoate concentrations from 300 to 700 mg litre^?1. The unit can be used at the dip site and the analysis is completed in 30 minutes.     

Depression of the minimum concentration of methyl bromide effective against diapausing warehouse moth larvae at 15°c by prior exposure at a moderate concentration

Warehouse moth (Ephestia elutella) larvae in diapause were exposed at 15°C to methyl bromide at 8 mg litre^?1 for 14.5 h and then immediately exposed at a lower concentration. The exposure at 8 mg litre^?1 killed 44–69% of the larvae treated. Subsequent concentrations down to 1.1 mg litre^?1 obeyed Haber's rule (concentration × time= k, a constant for mortality), but a higher concentration-time product (ct) was required for over 90% kill at 0.8 mg litre^?1. Only concentrations down to 1.9 mg litre^?1 obey Haber's rule if there is no prior exposure at a higher concentration. Although minimum effective concentrations are lower at 15°C than at 25°C, exposure at a higher concentration depresses the subsequent level to a similar extent at each temperature. The contribution to the efficacy of a treatment, of low concentrations persisting at the end of fumigation, is thus likely to be even greater at moderate to low temperatures than at 25°C. The implications for the development of resistance to methyl bromide are discussed.     

Minimum concentration levels of methyl bromide required for full efficacy against seven species of stored-product beetle at two temperatures

The dosages of methyl bromide required to control insect pests can be expressed as concentration, time (Ct) products for concentrations down to a certain minimal level, here defined as the efficacy threshold, below which Habers Ct rule (C×t=k,a constant for mortality) no longer applies. Twelve strains of seven species of stored-product beetle were tested to identify efficacy threshold concentrations at 15°C and 25°C. For each strain the efficacy threshold was higher at 25°C than at 15°C. Different species differed widely in the threshold levels identified. Strains with a higher than usual tolerance to methyl bromide than their standard stock counterparts had slightly higher efficacy thresholds at 25°C but not at 15°C. The order of tolerance of the standard stocks to methyl bromide at 15°C was Tribolium confusum> T. castaneum> Oryzaephilus surinamensis> Rhyzopertha dominica> Sitophilus granarius> S. zeamais> S. oryzae, and at 25°C Tribolium castaneum > T. confusum> R. dominica> O. surinamensis> S. granarius> S. zeamais> S. oryzae. The order of efficacy thresholds largely reflected the order of susceptibility, S. oryzae and S. zeamais having the lowest efficacy thresholds of about 0.6 mg litre^?1 at 15°C and 1.3-2.0 mg litre^?1 at 25°C, while Tribolium spp. had the highest, 1.3-2.0 mg litre^?1 at 15°C and 2.5-4.0 mg litre^?1 at 25°C.     

Effect of temperature on the toxicity of low concentrations of methyl bromide to diapausing larvae of the warehouse moth Ephestia elutella (Hübner)

The performance of low concentrations of methyl bromide against diapausing larvae of Ephestia elutella at 15 and 25°C was assessed in extended exposure periods. At concentrations of 1.9 mg litre^?1 and below, test batches required higher concentration-time (ct) products for 100% kill at 25°C than at 15°C. The minimum concentration at which the concentration: time relationship still applied was between 1.3 and 1.9 mg litre^?1 at 15°C, whereas at 25°C it was between 2.7 and 4.0 mg litre^?1. For many individuals within each population sample, however, lower concentrations at moderate dosage levels remained lethal. At 25°C, a ct product of about 90 mg litre^?1 h gave between 53 and 77% kill at 6.1, 4.0, 2.7 and 1.9 mg litre^?1. The trends observed suggest that the most tolerant members of the population have an enhanced ability to detoxify methyl bromide at the higher temperature. The implications of the results for the build-up of resistance and for practical control measures are discussed.     

Use of a field-scale biofilter for the degradation of the organophosphate insecticide coumaphos in cattle dip wastes

Insecticide wastes generated from livestock dipping operations are well suited for biodegradation processes since these wastes are concentrated, contained, and have no other significant toxic components. A field-scale biofilter capable of treating 15000-litre batches of dip waste containing the acaricide coumaphos was used to reduce the coumaphos concentration in two successive 11000-litre batch trials from 2000 mg litre^-1 to 10 mg litre^-1 in approximately 14 days at 25–29°C. Removal of coumaphos from the biofilter effluent is a function of both physical filtration and biodegradation by the biofilter. However, stoichiometric increases in chloride levels in the effluent as coumaphos concentrations decreased confirmed that coumaphos was being degraded by the biofilter rather than just being filtered out. In subsequent 5500-litre batch experiments, the addition of a vitamin supplement to the biofilter-treated dip resulted in a further decrease in coumaphos concentration to approximately 1 mg litre^-1. Results from incubations of two representative Texas soils with biofilter-treated dip spiked with [benzo-U-¹⁴C] coumaphos revealed that 32–36% of the spiked [¹⁴C] coumaphos was mineralized in the soils after 110 days at 30°C. © 1998 SCI.     

Effect of short exposures to a high concentration on the subsequent toxicity of low concentrations of methyl bromide to diapausing larvae of the warehouse moth,Ephestia elutella (Hübner)

Ephestia elutella larvae in diapause were exposed at 25°C to methyl bromide at 12 mg litre^?1 for 3.5 or 7.5 h and then immediately exposed to a lower concentration. The minimum effective concentration (that at which Haber's rule, concentration × time = k, a constant for mortality, still applied) was about 3 mg litre^?1 in tests with no previous exposure toa high concentration, but it was about 2.5 mg litre^?1 for individuals surviving a 3.5 h exposure to 12 mg litre^?1, and was about 1.6 mg litre^?1 for those surviving a 7.5 h exposure to 12 mg litre^?1. These exposures to 12 mg litre^?1, respectively, killed 2–20% and 50–75% of larvae exposed, and hence the smaller the proportion of survivors of exposure to a high concentration, the lower the minimum effective concentration needed against them. Thus the low concentration persisting at the end of a practical fumigation should contribute significantly to the success of the treatment and be much more effective than any similar low concentration present soon after the introduction of gas.     

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.     

Hydrolysis of the pyrethroid insecticide fenpropathrin in aqueous media

The hydrolysis of [¹⁴C] fenpropathrin ( I ) [(RS)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate] was studied in buffer solutions at pH 1.9–10.4, and in natural river and sea water at 25, 40, 55 and 65°C under laboratory conditions. The hydrolysis of I proceeded predominantly through neutral (pH independent) and base-catalysed processes in the regions below pH 3.9 and above pH 7.0, respectively, whereas both reactions occurred between pH 3.9 and 7.0. The rates of hydrolysis of I in buffer solutions were similar to those in one sample of river and one sample of sea water. If this obtains generally, it may be expected that the half-life of I in natural waters, normally within the range pH 5–9, will range from 1.54 to 1080 days at 40°C, 11.3 to 8520 days at 25°C and, by extrapolation of the data obtained in buffer solutions, 106 to 83 000 days at 10°C. The rate constants for hydrolysis of I in aqueous media can be expressed by: Where log k_N = 9.60–(5.56 × 10³ T^?1) and log k_B = 7.32–(2.56 × 10³ T^?1). The calculated rate constants were in good accord with the observed values in buffer solutions. Cleavage of the ester linkage was more rapid than hydration of the cyano group at any pH and temperature tested.     

Relation between volatility rating and composition of phenoxy herbicide ester formulations

A CIPAC/AOAC test with tomato plants is used to specify the volatility ratings of herbicide ester formulations. This work compares the tomato plant test with an alternative chemical one. The concentrations of esters and the effective molecular weight and density of each formulation were used with the ester vapour pressures to calculate its herbicide vapour pressure as complete, and evaporated formulations. The range was from 28.8 mPa (at 257deg;C) for a mixture of 2,4–D esters to 0–07 mPa (at 25°C) for a 2,4,5–T-(iso-octyl) formulation, as complete formulations, and 35-5 and 0–16 mPa (at 25°C) as evaporated ones. A value of 0–6 mPa (at 25°C) was selected on the basis of the tomato plant test as the cut-off area for low-volatile esters and is recommended to be included in specifications for herbicide esters. Formulations with a herbicide vapour pressure above 3.3 mPa (at 25°C) are high-volatile ones according to the tomato plant test, while between 0–6–3.3 mPa (at 25°C) is a borderline region where the test gives mixed results. Levels of 2,4–D-ethyl and methyl were added to pure 2–ethylhexyl esters of 2,4–D and a 2,4,5–T-(iso-octyl) formulation to find what level of contamination would change the rating of these esters from low to high volatile. Formulations of 2,4–D-(iso-octyl) should not contain more than 11 g litre^?1 2,4–D as methyl ester or 2.0 g litre^?1 2,4–D as ethyl ester. Formulations of 2,4,5–T-(iso-octyl) should not contain more than 26 g litre^?1 2,4–D as methyl ester or 4.7g litre^?1 2,4–D as ethyl ester.     

Atrazine hydrolysis. Part I: Proton catalysis at 25°C

Six new results have been obtained in an investigation of the catalysed hydrolysis of atrazine. A procedure was developed for determining rate constants from the first 20 mol% of the reaction. The reduced length of the experiments increased the experimental productivity and minimised the risk of sample deterioration. The proton catalysis rate was measured at 25°C, over the H⁺ concentration range of 1 to 10 mmol litre^?1. This shortened the extrapolation to the pH values of field conditions, and guaranteed the absence of doubly-protonated atrazine. Because spectrophotometry has been regarded as a controversial method for studying the hydrolysis kinetics of the 1,3,5-triazine herbicides, this method was re-examined. Excellent agreement was obtained from a comparison of the gas-liquid chromatographic and spectrophotometric methods of monitoring the kinetics experiments. Of the widely diverging relationships found in the literature for the extrapolation of laboratory half-lives to the pH range of field conditions, the one deduced from the reaction scheme of Plust et al. was found to be theoretically correct. Its parameters have been calibrated with several hundred experimental measurements. The proton is not the dominant catalytic agent in soils, but its calibration is essential for identifying those catalytic agents that are dominant. It has been deduced that the temperature dependence of the experimental rate constant is governed by the temperature responses of two parameters.     

N-Nitrosodimethylamine content of aqueous dimet hylamine and phenoxy herbicide/dimethylamine formulations during storage

N-Nitrosodimethylamine (NDMA) levels in samples of 600 g litre^?1 aqueous dimethylamine (DMA) solution stored at 4, 25 and 40°C, in formulations of the DMA salt of 2, 4-dichlorophenoxyacetic acid (2, 4-D) and of the DMA salt of 4-chloro-2-methylphenoxyacetic acid (MCPA) at 40°C were monitored using a gas-liquid chromatograph coupled with a thermal energy analyser (g.l.c./t.e.a.). The NDMA content of aqueous DMA at 4°C increased from 0.32μgg^?1 to 8.6μgg^?1 in 156 days. At 25°C it increased from 0.20μgg^?1 to 10.5 μgg^?1 in 156 days and at 40°C from 0.76μgg^?1 to 7.12μgg^?1 in 54 h. At 40°C, the NDMA in the 2, 4-D/DMAsalt increased from 0–53μgg^?1 to 2.79μgg^?1 in 96 days and in the MCPA/DMA salt from 0.48μgg^?1 to 5.51 μgg^?1 in 21 days.     

Transformation of aldicarb sulfoxide and aldicarb sulfone in four water-saturated sandy subsoils

The transformation of aldicarb sulfoxide and aldicarb sulfone was studied in incubations with water-saturated subsoils under simulated field conditions at 10°C. The subsoils were collected at four locations from beneath the water table at a depth of 2.5 to 3.5 m. In three of the subsoils, the half-life of sulfoxide, incubated at concentrations of 0.14-0.17 mg litre^?1, ranged from 0.7 to 2.8 years. At higher concentrations (8-13 mg litre^?1), its half-life ranged from 3.4 to 6.4 years. At the lower concentration, a large fraction of sulfoxide was transformed into sulfone. The rates of transformation of the sulfone at the lower concentration in the three subsoils corresponded to half-lives of 3.3 to 8.1 years, but in only one subsoil was a significant transformation rate (half-life 6.7 years) measured at the higher concentration during the 2.3-year incubation period. The half-lives at the lower concentrations were more like those in field studies, and perhaps would still underestimate transformation rates under field conditions. After a year, 2.5-15% of the higher sulfoxide and sulfone doses had been trapped as [¹⁴C] carbon dioxide. In the fourth subsoil, with more anaerobic conditions, the half-life of sulfoxide at both concentrations was less than 0.02 year and that of sulfone was about 0.04 year. Four or five radio-labelled transformation products could be traced in this subsoil and about half of the dose of both compounds was trapped as [¹⁴C] carbon dioxide.     

Partial purification and properties of an esterase from tomato cell suspension cultures hydrolysing the pyrethroid insecticide cyfluthrin

An esterase which hydrolyses the pyrethroid insecticide cyfluthrin, was isolated from tomato cell suspension cultures and purified 10-fold. The apparent molecular weight of the enzyme was estimated to be 32 000 Dalton, the pH-optimum 8-0, and the temperature optimum 35°C. The esterase showed a low substrate specificity and hydrolysed certain esters, e. g. ethyl 4-nitrobenzoate, p-nitrophenyl acetate and dinoseb acetate, whereas ethyl butyrate and the organophosphates demeton-S-methyl sulfoxide and paraoxon could not be hydrolysed. Because of the additional strong inhibition of the enzyme by these organophosphates the cyfluthrin hydrolase is suggested to belong to the B-esterase type. An apparent K_m-value of 6-25 × 10^?4 mol litre^?1 was obtained for p-nitrophenyl acetate as substrate.     

Conversion rates of aldicarb and its oxidation products in soils. II. Aldicarb sulphoxide

The loss of aldicarb sulphoxide was studied in incubation experiments with soil from four plough layers and two deeper layers. The loss during the 111 days of the experiment could be described by first-order kinetics. The half-lives at 15°C ranged from 20 days in a clay loam to 46 days in a peaty sand. The loss of sulphoxide in deeper layers was considerably slower than in the corresponding top layers of a soil profile. In soil from a silty layer at 70–90 cm depth the half-life was about 53 days. In soil from a sand layer at 90–110 cm depth a loss of only about 15% was measured after 111 days of incubation. First-order rate constants for sulphoxide conversion in a clay loam at 6, 15 and 25°C were found to be 0.009, 0.033, and 0.05 day^?1 respectively; in a greenhouse soil these rate constants were 0.0052, 0.019 and 0.04 day^?1 respectively. The fractions of aldicarb sulphoxide that were oxidised to sulphone at 15°C in soil from plough layers were computed to range from 0.52 to 0.76.     

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.     

A monoclonal antibody‐based ELISA for the analysis of the insecticide flucythrinate in environmental and crop samples

A competitive enzyme‐linked immunosorbent assay (ELISA) has been developed for the detection of the insecticide flucythrinate in environmental and food samples. Two types of haptens, the acid moiety that is the hydrolyzed product of flucythrinate, and the carboxylated propyl derivative of the alcohol moiety, were used to prepare monoclonal antibodies (MAbs). Five MAbs, which raised against the former hapten, were reactive with flucythrinate. Among them, MAb F1A27‐4 showed the highest activity toward flucythrinate, and did not cross‐react with other pyrethroids such as cycloprothrin, fenvalerate, fluvalinate, etofenprox and silafluofen. The assay conditions of indirect competitive ELISA with MAb F1A27‐4 were studied to optimize the detection of flucythrinate in environmental and food samples. Incubation at 4 °C in the assay buffer, pH 8, with 300 mM sodium chloride improved the sensitivity. The addition of rabbit serum albumin or rabbit antiserum and the presence of 50 ml litre^?1 of methanol reduced matrix effects of the samples. Under optimized conditions, the ELISA detected flucythrinate spiked in water, soil, and extracts of apple and tea samples down to 10 mg litre^?1, 0.2 mg litre^?1, 0.3 mg litre^?1 and 0.3 mg litre^?1, respectively. The mean recovery and CV ranged from 91% to 120% and from 5% to 12%, respectively. The ELISA results in apple samples correlated well with those from LC–MS analysis (r² = 0.99, n = 12). © 2001 Society of Chemical Industry     

Hydrolysis of 1, 3-dichloropropene in dilute aqueous solution

Hydrolysis of [¹⁴C]-radiolabeled 1, 3-dichloropropene (1, 3-D) was studied at pH 5, 7 and 9 at 10, 20 and 30°C in sterile buffered water. The rate of hydrolysis was independent of pH at each temperature, with measured half-lives of 3-1 (±0.l), 11.3 (±0.5) and 51 (±2.3) days at 30, 20 and 10°C, respectively. The activation energy for the hydrolysis reaction was determined to be 23.9 kcal mol^?1 deg^?1. One hydrolysis product was formed during the course of the study and was identified by co-chrornatography with analytical standards, using h.p.l.c., to be 3-chloroallyl alcohol. The alcohol appeared to be stable to further hydrolytic conversion and was formed in the same cis: trans ratio as in the initial 1, 3-D starting material, indicating essentially identical rates of hydrolysis for the cis and trans isomers of 1, 3-D.     

Partitioning of etofenprox under simulated California rice‐growing conditions

BACKGROUND: The pyrethroid insecticide etofenprox is of current interest to rice farmers in the Sacramento Valley owing to its effectiveness against the rice water weevil, Lissorhoptrus oryzophilus Kuschel. This study aimed to describe the partitioning of etofenprox under simulated rice field conditions by determining its Henry's law constant (H) (an estimate of volatilization) and organic carbon‐normalized soil–water distribution coefficient (K_oc) at representative field temperatures. A comparison of etofenprox and λ‐cyhalothrin is presented using a level‐1 fugacity model. RESULTS: Experimental determination of H revealed that etofenprox partitioned onto the apparatus walls and did not significantly volatilize; the maximum value of H was estimated to be 6.81 × 10^?1 Pa m³ mol^?1 at 25 °C, based on its air and water method detection limits. Calculated values for H ranged from 5.6 × 10^?3 Pa m³ mol^?1 at 5 °C to 2.9 × 10^?1 Pa m³ mol^?1 at 40 °C, based on estimated solubility and vapor pressure values at various temperatures. Log K_oc values (at 25 °C) were experimentally determined to be 6.0 and 6.4 for Princeton and Richvale rice field soils, respectively, and were very similar to the values for other pyrethroids. Finally, temperature appears to have little influence on etofenprox sorption, as the log K_oc for the Princeton soil at 35 °C was 6.1. CONCLUSION: High sorption coefficients and relatively insignificant desorption and volatilization of etofenprox suggest that its insolubility drives it to partition from water by sorbing to soils with high affinity. Offsite movement is unlikely unless transported in a bound state on suspended sediments. Copyright © 2009 Society of Chemical Industry     

Determination of residual 2,4,5-T in vegetables by high performance liquid chromatography with ultraviolet and fluorometric detection after derivatization with 2-(2,3-naphthalimino)ethyl trifluoromethanesulfonate (NE-OTf)

2,4,5-T was extracted with acetone at below pH 1·0 and the extract was concentrated. After adding 100 g litre^-1 sodium chloride solution to the residual solution, 2,4,5-T was extracted with ethyl acetate+hexane (20+80 by volume). The extract was evaporated to dryness and the residue was dissolved in acetonitrile. 18-crown-6, potassium fluoride and NE-OTf were added to the acetonitrile solution and then allowed to react at 50°C for 20 min. The product was injected to a HPLC with ultraviolet detection operated at 259 nm and fluorometric detection at 394 nm emission and 259 nm excitation. The determination limits of the 2,4,5-T derivative in the sample were 20 μg litre^-1 with UV detection and 10 μg litre^-1 with fluorometric detection. © 1997 SCI.     

Preventive and curative activity of postharvest potassium silicate treatments to control green and blue molds on orange fruit

Preventive and curative antifungal activities of postharvest treatments with potassium silicate (PSi) against green (GM) and blue (BM) molds were evaluated on oranges (cvs. ‘Valencia’ or ‘Lanelate’) artificially inoculated in rind wounds with Penicillium digitatum and P. italicum, respectively. The most effective PSi concentration, the effect of fungal inoculum concentration, and the influence of temporal and spatial factors on antifungal activity were assessed in in vivo primary screenings. After 6 days of incubation at 20 °C, significant preventive (treatment before fungal inoculation) and curative (treatment after inoculation) activities against GM and BM were observed with PSi at 90 mM (GM and BM incidence reductions of 23 and 52 %, and 23 and 40 %, respectively). In preventive tests, the effectiveness of PSi was influenced by inoculum concentration (10³, 10⁴, 10⁵, or 10⁶ spores ml^-1), but not by the distance between treatment and inoculation sites (10, 20 or 30 mm). PSi applied about 2 h before inoculation showed higher preventive activity than applied before 24, 48 or 96 h. In order to determine the best dip treatment conditions, PSi at 90 mM was tested at 20 or 50 °C for 60 or 150 s in small-scale trials with ‘Lanelate’ oranges artificially inoculated before or after the treatment and incubated for 7 days at 20 °C. Dips at 20 °C for 60 s were selected and subsequently applied on inoculated ‘Valencia’ oranges stored at 5 °C and 90 % RH for up to 6 weeks. Curative postharvest dips effectively reduced the incidence and severity of both GM and BM during cold storage, while preventive dips significantly reduced the severity but not the incidence. Overall, postharvest PSi treatments showed potential as a new tool to be part of non-polluting strategies to control penicillium decay of citrus fruit.