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PubMed2005

The influence of post-exposure temperature on the toxicity of insecticides to Ostrinia nubilalis (Lepidoptera: Crambidae).

The influence of post-treatment temperature on the toxicities of two pyrethroids (lambda-cyhalothrin and bifenthrin), a carbamate (methomyl) and a spinosyn (spinosad) to Ostrinia nubilalis (Hubner) larvae was evaluated in laboratory assays. From 24 to 35 degrees C, the toxicities of the pyrethroids decreased 9.5- and 13.6-fold while spinosad toxicity decreased 3.8-fold. The toxicity of methomyl did not change significantly. The results demonstrate that the most effective insecticide against a pest may vary with environmental conditions. In situations where comparable products from multiple insecticide classes are available, temperature should be included as a factor in the decision-making process.

Animals↗
PubMed2006

Pesticide detoxifying functions of N-halamine fabrics.

Halamine structures incorporated on polyester/cotton fabrics were able to detoxify oxime carbamate pesticides that contain thio bonds rapidly upon contact. The reaction was endothermic, and the detoxification rate was in first order to concentrations of the pesticides. Aldicarb was degraded in a much faster rate than that of methomyl by the halamine fabrics. The reactivity of halamine structures was different, and imide halamine was more reactive than amine halamine. The detoxification was an oxidative reaction on the sulfur atom existing in both aldicarb and methomyl. The same halamine structures were unable to effectively react with carbaryl and carbofuran, which are aromatic carbamates and do not contain any thio bonds.

Aldicarb↗
PubMed2005

Effect of dislodging techniques on foliar residue determination for agricultural crops.

The Agricultural Reentry Task Force (ARTF) conducted a study to determine whether different dislodgeable foliar residue (DFR) techniques had any effect on the amount of residues dislodged from the leaves of vegetable crops. Four previously employed techniques were evaluated with two chemicals (carbaryl and methomyl) on two crops (cabbage and lettuce). Carbaryl, a moderately water-soluble chemical, was applied at a rate of 2.0 lbs active ingredient/acre (lb ai/A) while methomyl, a highly water soluble chemical, was applied at a rate of 0.9 lb ai/A. One day after application, leaf punches were collected and the residues were dislodged following one of four techniques that differed in the number of dislodgings per sample, the duration of dislodging, the solution volume, and/or the type of solution used. The results indicated that three of the techniques gave similar results, whereas a fourth gave marginally lower results.

Carbaryl↗
PubMed2006

Application of dual counter-current chromatography for rapid sample preparation of N-methylcarbamate pesticides in vegetable oil and citrus fruit.

Dual counter-current chromatography (dual CCC) has been successfully applied to rapid sample preparation for the simultaneous determination of residual carbaryl, fenobucarb and methomyl in vegetable oil and citrus fruit. The citrus fruit samples were extracted with n-hexane solution containing stable isotopically labeled internal standards (methomyl-d3, fenobucarb-d3 and carbaryl-d9), and applied to dual CCC using a two-phase solvent system of n-hexane-acetonitrile to purify the carbamate pesticides from aliphatic sample matrix. The coiled column was rotated at 420 rpm, the lower mobile phase was introduced through the head toward the tail, and the upper mobile phase in the opposite direction. Due to the high partition efficiency of dual CCC, the lower phase fraction collected from 2 to 5 min after injection could be subjected to flow-injection tandem mass spectrometry directly after concentration. Repetitive sample injection can be performed at high reproducibility without a risk of contamination from the compounds retained in the column.

Carbamates↗
PubMed2003

Considerations on ultra trace analysis of carbamates in water samples.

A new routine method for the ultra trace analysis of carbamates in water samples is presented, using solid-phase extraction followed by high-performance liquid chromatography coupled to atmospheric pressure electrospray ionisation mass spectrometry (SPE-LC-ESI-MS). Instrumental conditions of LC-ESI-MS in the selected ion monitoring (SIM) mode, showed excellent linear response for the six N-methyl carbamates studied (aldicarb, carbaryl, carbofuran, methomyl, oxamyl and pirimicarb) in the range from 1 to 50 microg/l and a precision having a relative standard deviation below 7.8% was achieved. Instrumental limits of detection of 0.10 microg/l were found for these carbamates, with the exception of methomyl for which 0.50 microg/l was measured. The SPE assays were shown to be easy, fast, very sensitive, requiring a low volume (50 ml) of water sample. For laboratory-spiked water samples having 0.03 and 0.30 microg/l of individual N-methyl carbamates, higher selectivities were achieved in cartridges having octadecylsilica, polystyrene-divinylbenzene and N-vinylpyrrolidane-divinylbenzene as solid phases, for which reasonable average recoveries were obtained. Ten replicates using octadecylsilica SPE cartridges, showed average recoveries between 73.7 and 92.6% with a relative standard deviation lower than 14.7%. The present methodology evidences good robustness, accuracy and precision for monitoring of N-methyl carbamates in water samples, and is shown to be a suitable alternative to replace the currently dedicated analytical systems. The limits of detection for the analysis of N-methyl carbamates in water samples reached in the present methodology (0.5 to 3 ng/l), clearly cover the maximum concentration admissible for pesticides, established by the European Union directive on water quality.

Aldicarb↗
PubMed2002

Toxicity assays: a way for evaluating AOPs efficiency.

The technical feasibility and performance of photocatalytic degradation of aqueous methomyl (50 mg/L) have been studied at pilot scale in two well-defined systems of special interest because natural-solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. The pilot plant is made up of compound parabolic collectors specially designed for solar photocatalytic applications. Experimental conditions allowed pesticide disappearance, degree of mineralisation and toxicity achieved in the two photocatalytic systems to be compared. Total disappearance of methomyl is attained by photo-Fenton in 60 min and by TiO2 in 100 min. Hundred percent of nitrogen and sulphur are recovered as ammonium and sulphate. By contrast, complete mineralisation of total organic carbon (TOC) is not achieved even after quite a long time (more than 300 min). Three different bioassays (Vibrio fischeri, Daphnia magna and a Microalga) have been used for testing the progress of toxicity during treatment. All remained toxic down to very low-pesticide concentrations and in some bioassays were still toxic after total disappearance of the pesticide. Only if treatment is maintained throughout enough mineralisation (i.e. TOC disappearance), the toxicity is reduced to below the threshold (EC50%).

Animals↗
PubMed2005

Dislodgeable foliar residues are lognormally distributed for agricultural re-entry studies.

The Agricultural Reentry Task Force (ARTF) conducted a study to determine if dislodgeable foliar residues (DFR) are either normally or lognormally distributed. This is important because the data are used with worker exposure data, which generally appear to be lognormally distributed, to calculate transfer coefficients that will be used to assess farm worker re-entry exposure. Two chemicals were used for this study. Carbaryl, a moderately water-soluble chemical, was applied to cabbage at a rate of 2.0 lbs active ingredient/acre (lb ai/A), while methomyl, a highly water soluble chemical, was applied to cabbage at a rate of 0.9 lb ai/A. The residues were dislodged following an ARTF standardized procedure of collecting leaf punches and shaking in a solution of 0.01% Aerosol OT 75. A total of 28 samples were analyzed for each chemical. The mean+/-SD residue of the carbaryl samples was higher than that for methomyl (511+/-196 and 170+/-71 mug per sample, respectively). However, several types of statistical analyses of the data indicated that, for both chemicals, the residues are lognormally distributed.

Agriculture↗
PubMed1991

Biochemical studies on the terrestrial snail, Eubania vermiculata (Müller) treated with some pesticides.

The in vivo effects of methomyl, thiodicarb and metaldehyde on total soluble proteins, total lipids and glycogen content, in addition, the activity of glutamic oxaloacetic transaminase, (GOT), (GPT) glutamic pyruvic transaminase and catalase (CAT) enzymes of terrestrial E. vermiculata snails was studied. The experimental snails were treated with low concentration of 0.2% brain bait w/w of the pesticides for a period of 1,3,5,7 and 10 days. The results showed that methomyl and thiodicarb lead to significant reduction in total soluble proteins, lipids, and glycogen content, while significant increases in the activity of all enzymes tested were noted. Metaldehyde treatment showed no significant effect on total soluble proteins, lipids and GOT level, whereas a significant increase in GPT and CAT enzymes was observed. Also, metaldehyde resulted a significant reduction in glycogen content of snails.

Acetaldehyde↗
PubMed2001

Effects of various insecticides on the development of the egg parasitoid Trichogramma dendrolimi (Hymenoptera: Trichogrammatidae).

The toxicity of six insecticides, acephate, methomyl, ethofenprox, cartap, chlorfluazuron, and Bacillus thuringiensis (Bt) was tested on different developmental stages of the egg parasitoid, Trichogramma dendrolimi (Matsumura). Each of the insecticides tested showed different degrees of toxicity to the parasitoid, Ethofenprox showed the highest toxicity and cartap showed relatively higher toxicity compared with the other insecticides. The development of the parasitoids treated with these two insecticides was normal, similar to that of the control group. Only the emergence of adult wasps from host eggs was disturbed. Emergence of the host, Mamestra brassicae larva was reduced following treatment with ethofenprox, cartap and methomyl. However, adult female wasps, which emerged from host eggs treated with the insecticides had the ability to oviposit normally.

Animals↗
PubMedDate not supplied

[Application of chemiluminescent technique for determination of Daphnia magna sensitivity to various types of toxic agents].

The character and intensity of activated chemiluminescence of Daphnia living medium are investigated depending on the effect on them of various concentration different in nature toxic substances, such, as potassium bichromate, methomyl and tween-80. It is shown, that the toxic influence of these agents can be defined by registration of stimulating effect of Daphnia's exometabolites on the process of chemiluminescence. The sensitivity of the method makes: for potassium chromate--0.005 mg/l, methomyl--0.0013 mg/l and tween-80--0.1 mg/l.

Animals↗
PubMed1988

Joint action of nuclear polyhedrosis virus and chemical insecticides against the black cutworm, Agrotis ipsilon (Hufn.).

A polyhedrosis virus disease was isolated from the larvae of Agrotis ipsilon. Isolation of causative agent from the infected larvae again showed to be positive. Microscopic examination of the infected larvae (by means of a light microscope) gave an evidence of the development of the polyhedral inclusion bodies (PIB) in all typical tissues where the virus is known to develop. Examination by an electron microscope showed various irregular shaped polyhedra; their diameter being about 1.5 to 3.5 mu. Most of these polyhedra were hexagonal and they measured about 2.2 mu. Experimental studies were conducted to investigate its pathogenicity alone and when combined with chemical insecticides. The joint action of the nuclear polyhedrosis virus of A. ipsilon (AINPV) combined with four chemical insecticides namely Fenvalerate, Decamethrin, Cypermethrin and Methomyl was assessed against the second instar larvae of A. ipsilon. Results showed that Decamethrin was the most toxic compound followed by Cypermethrin and Fenvalerate while Methomyl was the least toxic, the median lethal concentrations (LC50) were 0.25, 0.77, 14 and 450 ppm, respectively. The LC50 value of AINPV was 12 x 10(6) PIB/ml. Mixtures containing sublethal concentrations (LC25 and less) of both AINPV and any of the tested insecticides showed synergistic effects. On the other hand, an additive effect was observed with combinations containing doses of chemical insecticides over the range between LC25 and LC50 values.

Animals↗
PubMed2002

Effects of currently used pesticides in assays for estrogenicity, androgenicity, and aromatase activity in vitro.

Twenty-four pesticides were tested for interactions with the estrogen receptor (ER) and the androgen receptor (AR) in transactivation assays. Estrogen-like effects on MCF-7 cell proliferation and effects on CYP19 aromatase activity in human placental microsomes were also investigated. Pesticides (endosulfan, methiocarb, methomyl, pirimicarb, propamocarb, deltamethrin, fenpropathrin, dimethoate, chlorpyriphos, dichlorvos, tolchlofos-methyl, vinclozolin, iprodion, fenarimol, prochloraz, fosetyl-aluminum, chlorothalonil, daminozid, paclobutrazol, chlormequat chlorid, and ethephon) were selected according to their frequent use in Danish greenhouses. In addition, the metabolite mercaptodimethur sulfoxide, the herbicide tribenuron-methyl, and the organochlorine dieldrin, were included. Several of the pesticides, dieldrin, endosulfan, methiocarb, and fenarimol, acted both as estrogen agonists and androgen antagonists. Prochloraz reacted as both an estrogen and an androgen antagonist. Furthermore, fenarimol and prochloraz were potent aromatase inhibitors while endosulfan was a weak inhibitor. Hence, these three pesticides possess at least three different ways to potentially disturb sex hormone actions. In addition, chlorpyrifos, deltamethrin, tolclofos-methyl, and tribenuron-methyl induced weak responses in one or both estrogenicity assays. Upon cotreatment with 17beta-estradiol, the response was potentiated by endosulfan in the proliferation assay and by pirimicarb, propamocarb, and daminozid in the ER transactivation assay. Vinclozolin reacted as a potent AR antagonist and dichlorvos as a very weak one. Methomyl, pirimicarb, propamocarb, and iprodion weakly stimulated aromatase activity. Although the potencies of the pesticides to react as hormone agonists or antagonists are low compared to the natural ligands, the integrated response in the organism might be amplified by the ability of the pesticides to act via several mechanism and the frequent simultaneous exposure to several pesticides.

Animals↗
PubMed1995

The relationship between the mitochondrial gene T-urf13 and fungal pathotoxin sensitivity in maize.

Mitochondria isolated from maize containing cms-T cytoplasm are specifically sensitive to pathotoxins (T-toxins) produced by the fungi Bipolaris maydis race T and Phyllosticta maydis. T-toxins interact with a 13 kDa membrane-bound toxin receptor protein, URF13, to produce hydrophillic pores in the membrane. Expression of URF13 in Escherichia coli produces bacterial cells that form hydrophillic pores in the plasma membrane when exposed to T-toxin or methomyl. Topological studies have established that URF13 contains three membrane-spanning alpha-helices, two of which are amphipathic and may contribute to pore formation. URF13 specifically binds T-toxin in a cooperative manner. Oligonucleotide-directed mutagenesis of URF13 led to the isolation of methomyl/T-toxin-resistant mutations at 39 separate positions throughout the URF13 primary sequence. Chemical cross-linking of URF13 demonstrated the presence of URF13 oligomers and established that the pore-forming species is oligomeric. The ability of the carboxylate-specific reagent, dicyclohexycarbodiimide to cross-link URF13 has been used in conjunction with site-directed mutagenesis to establish that the URF13 tetramer has a central core consisting of a four-alpha-helical bundle that may undergo a conformational change after T-toxin or methomyl binding. Experimental evidence indicates that URF13 acts as a ligand-gated, pore-forming T-toxin receptor.

Amino Acid Sequence↗
PubMed2005

Evaluation of a new hypercrosslinked polymer as a sorbent for solid-phase extraction of polar compounds.

A new hypercrosslinked polymer (HXLGp) with hydrophilic character due to the presence of hydroxyl moieties has been tested as a sorbent for the solid-phase extraction (SPE) of several polar compounds from water samples. This new sorbent enables the on-line extraction of 300 ml of sample with recoveries higher than 80% for polar compounds such as oxamyl, methomyl or desisopropylatrazine (DIA). The HXLGp has also been compared to other commercially available sorbents such as Oasis HLB (hydrophilic macroporous), to hydrophobic hypercrosslinked resins and to a previously synthesized sorbent based on N-vinylimidazole-divinylbenzene. The results are consistently better with the new synthesized sorbent. The method was successfully applied to the on-line SPE-HPLC of tap and river water samples. The validation with river water samples provided good linearity range and detection limits between 0.03 for methomyl and 4-nitrophenol (4NP) to 0.2 microg l(-1) for phenol (Ph).

Chromatography↗
PubMed2004

Progress in pesticide and POPs hair analysis for the assessment of exposure.

The present paper reviews the work that has been done in the field of pesticide and persistent organic pollutants (POPs) hair analysis during the last 15 years. It summarizes the compounds of interest, the methods of analyte extraction from the hair matrix, the analytical techniques employed and the results obtained. The most widely studied POPs are the polychlorinated dibenzodioxins (PCDDs), the dibenzofurans (PCDFs) the co-planar biphenyls (co-PCBs) and total biphenyls (PCBs). The most widely studied pesticides are the organochlorine ones, like the hexachlorocyclohexanes and the DDTs, which nowadays are only found as environmental pollutants, some organophosphates, selected pyrethroids and the carbamate methomyl. The most widely applied technique was gas chromatography (GC) coupled to mass spectrometry (MS). Other detectors like the ECD in the case of organochlorine analysis and the NPD in the case of organophosphate analysis were also used. The presented data concern human and animal studies. The levels of DDTs detected in hair were between 19 and 400 ng/g, of co-PCBs 0.27 and 0.45 ng/g, of total PCBs 5-13 ng/g of PCDDs and PCDFs 0.1-10 pg/g of lindane 20-400 ng/g of HCHs 14-40 ng/g of diazinon 110-520 ng/g and of methomyl 900-1800 ng/g. These results strongly support the possibility of using hair as a suitable indicator for the assessment of long-term exposure to POPs and pesticides.

Animals↗
PubMed1998

Exposure and risk estimation for pesticides in high-volume spraying.

During twenty applications with a spray pistol of methomyl to chrysanthemums, inhalation exposure as well as potential and actual dermal exposure were monitored using the 'whole-body'-method. On the basis of the exposure data, in terms of exposure to the liquid formulation and the spray liquid, the possible health risk for methomyl and thirteen other pesticides, frequently used in ornamentals, was indicatively assessed. From the No-Observed-Adverse-Effect-Level (NOAEL) in animal experiments an Indicative Limit Value (ILV) was derived. The ILV is considered indicative for the limit of daily exposure for a worker which probably gives no rise to adverse health effects. This value is a rough approximation since the database for a proper assessment of such a value is generally incomplete. Assuming that exposure is independent of the pesticide, using a suitable format, the actual observed exposure can be compared with the ILV. To reduce the dermal exposure levels below the ILV the exposure of especially the hands has to be reduced e.g. by using impermeable gloves.

Agriculture↗
PubMed2004

N-methyl carbamate concentrations and dietary intake estimates for apple and grape juices available on the retail market in Canada.

Infants and young children consume fruit juices and drinks at rates exceeding those of older children and adults. Carbamate pesticides are known to be used on a broad spectrum of crops, including orchard and vine crops such as apples and grapes. Concern over potential exposure to these acutely toxic pesticides by infants and young children has increased in the last decade. Liquid chromatography with fluorescence detection was used to determine the concentrations of seven N-methyl carbamates and three transformation products in domestic and imported apple and grape juices collected across Canada. Carbaryl was the most frequently (58.6%) detected N-methyl carbamate in juice samples studied. It was observed more frequently in grape juices than in apple or mixed juices. Oxamyl and methomyl were detected in apple juice samples, although they were below detection limits in all grape and mixed juice samples analysed. Maximum levels of carbaryl, methomyl and oxamyl were 93, 6.7 and 4.6 ng ml(-1), respectively. All other analytes were not present in any juice sample at concentrations above the method detection limit (0.3 ng ml(-1)). In all cases, N-methyl carbamate residues were well below the maximum residue limit established for apples and grapes in the Canadian Food and Drug Regulations. No estimated dietary intakes were above the acceptable daily intakes in any age-sex category, where an acceptable daily intake has been proposed. Carbaryl short-term intake estimates were calculated and all were below the proposed acute reference doses.

Beverages↗
PubMed2003

Residual susceptibility of the red imported fire ant (Hymenoptera: Formicidae) to four agricultural insecticides.

The red imported fire ant, Solenopsis invicta Buren, is an abundant predator in cropping systems throughout its range. It has been documented to be an important predator of numerous crop pests, as well as being an agricultural pest itself. Information on the impact of insecticides on natural enemies such as fire ants is necessary for the integration of biological and chemical control tactics in an effective pest management program. Therefore, a residual vial bioassay was developed to determine the concentration-mortality responses of S. invicta workers to four commonly used insecticides: acephate, chlorpyrifos, methomyl and lambda-cyhalothrin. Fire ant workers showed a mortality response to serial dilutions to all four chemicals. Methomyl (LC50 0.04 microg/vial, fiducial limits 0.03-0.06) was the most toxic, followed by chlorpyrifos (LC50 0.11 microg/vial, fiducial limits 0.07-0.17) and acephate (LC50 0.76 microg/vial, fiducial limits 0.50-1.04). Of the chemicals assayed, it took a much higher concentration of lambda-cyhalothrin (LC50 2.30 microg/vial, fiducial limits 1.57-3.59) to kill 50% of the workers compared with the other three chemicals. The results of this study demonstrate the wide range in responses of fire ants to four insecticides that are labeled and commonly used on numerous agricultural crops throughout the United States. These results further suggest the possibility of using a discriminating dose of lambda-cyhalothrin to control the target pest species while conserving fire ants in the agricultural systems in which their predatory behavior is beneficial to the integrated pest management program.

Animals↗