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Headspace solid-phase microextraction in combination with gas chromatography-mass spectrometry for the rapid screening of organophosphorus insecticide residues in strawberries and cherries.

A headspace solid-phase microextraction (HS-SPME) method in combination with GC-MS was used for the extraction and quantification of diazinon, fenitrothion, fenthion, parathion ethyl, bromophos methyl, bromophos ethyl and ethion. The method was developed using a 100-microm poly(dimethylsiloxane) fiber. The obtained results showed higher responses of the insecticides after addition of aliquots of water and solvent to the fruit samples. Calibration curves that were constructed for the analytes spiked into strawberry and cherry samples followed linear relationships with good correlation coefficients (R2 > 0.986). Linearity range was between 50 and 500 microg/kg and the precision was found to be lower than 15% when applying the optimized HS-SPME procedure to fruit samples. Limits of detection in both strawberry and cherry samples using GC-MS (selected ion monitoring mode) were below 13 microg/kg. Moreover, the HS-SPME method was applied to the analysis of fruit samples and compared with liquid-liquid extraction. Results obtained in this study were in good agreement with those obtained using liquid-liquid extraction demonstrating that the recommended procedure was a fast, accurate and stable sample pretreatment method obtaining good efficiency for the extraction of organophosporus insecticides from strawberries and cherries.

Fragaria↗

High-performance liquid chromatographic determination of benzoylurea insecticides residues in grapes and wine using liquid and solid-phase extraction.

A method for the determination of the benzoylurea insecticides diflubenzuron, triflumuron, teflubenzuron, lufenuron and flufenoxuron in grapes and wine by HPLC has been developed and validated. Grape samples (50 g) were homogenized and extracted with ethyl acetate-sodium sulfate and further cleaned-up by solid-phase extraction on silica sorbent. Wine samples (10 ml) diluted with water (1:3) were solid-phase extracted on an octadecyl sorbent using methanol as the eluent. The pesticides were separated on a reversed-phase octadecyl narrow-bore column by gradient elution and the residues were determined with a UV diode array detector. The calibration plots were linear over the range 0.05-5 micrograms/ml. Recoveries of benzoylurea pesticides from spiked grapes (0.02-2.0 mg/kg) and wine (0.01-0.2 mg/l) were 85.8-101.6% and 69.1-104.8%, respectively, and the limits of quantification for these insecticides were < 0.01 mg/kg for grapes and < 0.01 mg/l for wine. The method was applied to the determination of flufenoxuron and teflubenzuron residues in grapes from treated fields and in produced wine.

Calibration↗

Inhibition of 17 beta-estradiol and progesterone activity in human breast and endometrial cancer cells by carbamate insecticides.

Using a combination of in vitro assays we have examined the capacities of contemporary-exposure chemicals to modulate human estrogen and human progesterone receptor (hER and hPR) activity in human breast and endometrial cancer cells. The carbamate insecticides aldicarb, Baygon (propoxur), bendiocarb, carbaryl, methomyl, and oxamyl were used in this study. The carbamates alone weakly activated estrogen- or progesterone-responsive reporter genes in breast and endometrial cancer cells. All of the carbamates decreased estradiol- or progesterone-induced reporter gene activity in the breast and endometrial cancer cells. In whole cell competition binding assays, the carbamates demonstrated a limited capacity to displace radiolabeled estrogen or progesterone from ER or PR. Based on the results presented here, the carbamate insecticides may represent a class of chemicals which function through a mechanism separate from ligand-binding and, therefore, may act as general endocrine modulators in mammalian cells.

Binding, Competitive↗

Occurrence of the insecticidal 16,17-didehydro-16(E)-stemofoline in Stemona collinsae.

The occurrence of two alkaloids, 16,17-didehydro-16(E)-stemofoline and its isomer at C-4, 16,17-didehydro-4(E)-16(E)-stemofoline, were found together with a known insecticidal compound, stemofoline, in Stemona collinsae. The 16,17-didehydro-16(E)-stemofoline displayed higher insecticidal and antifeedant activities against the diamondback moth larvae than stemofoline.

Animals↗

Insecticidal flavaglines and other compounds from Fijian Aglaia species.

Bioassays with lipophilic crude extracts of four Fijian Aglaia species against Spodoptera littoralis displayed strong insecticidal activity for A. basiphylla and A. gracilis, whereas A. archboldiana and A. vitiensis did not have any significant effects. The insect toxicity of A. basiphylla was caused by the well known benzofuran flavaglines rocaglamide, desmethylrocaglamide and aglafoline. In contrast, A. gracilis contained four related pyrimidinone derivatives in the root and stem bark, including two new congeners named marikarin and 3'-hydroxymarikarin. Moreover, two new putrescine bisamides, secoodorine and secopiriferine, a new benzopyran flavagline. desacetylaglain A. and a new norsesquiterpene were isolated from the leaves together with three known bisamides and 3-hydroxy-5,7,4'-trimethoxyflavone. The structures of the new compounds were elucidated by spectroscopic methods. Comparative feeding assays within the active pyrimidinone flavaglines showed that the free hydroxy group in aromatic ring A of marikarin diminishes insecticidal activity.

Benzofurans↗

Insecticidal compounds from Kalanchoe daigremontiana x tubiflora.

Methyl daigremonate, an insecticidal bufadienolide, was isolated from the leaves of Kalanchoe daigremontianaxtubiflora (Crassulaceae) along with four known bufadienolides. Its structure was established by spectroscopic analysis, and insecticidal activities were assessed against the third instar larvae of silkworm (Bombyx mori). The results suggest that the orthoester and alpha-pyrone moieties played an important role in the activity.

Animals↗

Insecticidal pyrido[1,2-a]azepine alkaloids and related derivatives from Stemona species.

Eight new alkaloids, the pyrido[1,2-a]azepines stemokerrin, methoxystemokerrin-N-oxide, oxystemokerrin, oxystemokerrin-N-oxide, and pyridostemin, along with the pyrrolo[1,2-a]azepines dehydroprotostemonine, oxyprotostemonine, and stemocochinin were isolated from four Stemona species together with the known compounds protostemonine, stemofoline, 2'-hydroxystemofoline, and parvistemonine. Their structures were elucidated by 1H and 13C NMR including 2D methods and two key compounds additionally by X-ray diffraction. Besides the formation of a six membered piperidine ring, additional oxygen bridges and N-oxides contributed to structural diversity. The co-occurrence of pyrrolo- and pyridoazepines suggested biosynthetic connections starting from more widespread protostemonine type precursors. Bioassays with lipophilic crude extracts against Spodoptera littoralis displayed very strong insecticidal activity for the roots of S. curtisii and S. cochinchinensis, moderate activity for S. kerrii, but only weak effects for the unidentified species HG 915. The insect toxicity was mainly caused by the accumulation of stemofoline, oxystemokerrin, and dehydroprotostemonine displaying two different modes of action. Based on the various insecticidal activities of 13 derivatives structure-activity relationships became apparent.

Alkaloids↗

Partial synthesis of 3-O-vanilloylveracevine, an insecticidal alkaloid from Schoenocaulon officinale.

3-O-Vanilloylveracevine has been synthesized for the first time in 70% overall yield by conversion of veracevine into its 3-O-(4-benzyloxy-3-methoxybenzoate) followed by catalytic hydrogenation. The insecticidal activity of the semisynthetic substance against three pest species is inferior to that of cevadine and veratridine, the major components of the insecticidal sabadilla alkaloid mixture.

Animals↗

Evaluation of a prototype long-lasting insecticide-treated mosquito net under field conditions in rural Burkina Faso.

Insecticide measurements and standard World Health Organization bioassays on random samples of new unwashed, traditionally washed and up to 18 months field-used 'long-lasting' deltamethrin treated mosquito nets demonstrated a rapid reduction of efficacy under field conditions. The technology of 'long-lasting' insecticide-treatment needs much improvement.

Animals↗

Comparison of the effect of insecticide-treated bed nets and DDT residual spraying on the prevalence of malaria transmitted by Anopheles anthropophagus in China.

In order to improve the control of malaria in a problem part of Hubei Province, China, where Anopheles anthropophagus is the vector of Plasmodium vivax, insecticide treatment of bed nets was introduced. The people were given the choice of DDT residual spraying, which had been used for many years, or deltamethrin treatment of their bed nets. Two counties, in which these 2 different methods had been introduced, and an untreated area were evaluated. DDT house spraying and insecticide treated bed nets were equally effective, but deltamethrin treatment was cheaper and so was considered the method of choice.

Bedding and Linens↗

Purification and amino acid sequence of a highly insecticidal toxin from the venom of the brazilian spider Phoneutria nigriventer which inhibits NMDA-evoked currents in rat hippocampal neurones.

A new insecticidal toxin Tx4(5-5) was isolated from the fraction PhTx4 of the venom of the spider Phoneutria nigriventer by reverse phase high performance liquid chromatography (HPLC) and anion exchange HPLC. The complete amino acid sequence determined by automated Edman degradation showed that Tx4(5-5) is a single chain polypeptide composed of 47 amino acid residues, including 10 cysteines, with a calculated molecular mass of 5175 Da. Tx4(5-5) shows 64% of sequence identity with Tx4(6-1), another insecticidal toxin from the same venom. Tx4(5-5) was highly toxic to house fly (Musca domestica), cockroach (Periplaneta americana) and cricket (Acheta domesticus ), producing neurotoxic effects (knock-down, trembling with uncoordinated movements) at doses as low as 50 ng/g (house fly), 250 ng/g (cockroach) and 150 ng/g (cricket). In contrast, intracerebroventricular injections (30 microg) into mice induced no behavioural effects. Preliminary electrophysiological studies carried out on whole-cell voltage-clamped rat hippocampal neurones indicated that Tx4(5-5) (at 1 microM) reversibly inhibited the N-methyl-D-aspartate-subtype of ionotropic glutamate receptor, while having little or no effect on kainate-, alpha-amino-3-hydroxy-5-methyl-4-isoxazole-propionic acid- or gamma-aminobutyric acid-activated currents.

Amino Acid Sequence↗

A correlation between the dissipation of insecticides and rhizosphere microflora of Abelmoschus esculentus (L.) Moench.

A study to understand the relationship between the dissipation of aldicarb and disulfoton in the rhizosphere region of bhendi and the microbial population revealed a negative correlation between the fungal and Azotobacter population and the residues of both insecticides. However, no definite correlation could be recorded between the populations of bacteria and actinomycetes and the residues of the insecticides.

Actinomycetales↗

Bioconcentration of the insecticide pyridaphenthion by the green algae Chlorella saccharophila.

A study was undertaken to examine the uptake of the organophosphate insecticide pyridaphenthion in the chlorophyta Chlorella saccharophila. Algae cultures were exposed to the initial nominal concentration 10.0 mg l(-1) pyridaphention during seven days. The insecticide bioconcentrates in the biomass to the highest level of 441.5 +/- 25.9 mg kg(-1) on the fifth day of exposure and was followed by a decrease to 76.6 +/- 5.1 mg kg(-1) on the seventh day. A model was constructed to describe the dynamic process, which estimated a bioconcentration factor (BCF) equal to 28. The study demonstrates the potential of accumulation of pyridaphenthion in aquatic organisms and helps to expand the pyridaphenthion toxicity database. The replacement of fenitrothion by pyridaphenthion concerning their use in rice flooded cultures is discussed.

Absorption↗

Organochlorine insecticides, polychlorinated biphenyls, and metals in water, sediment, and green frogs from southwestern Michigan.

In an attempt to explain the etiology of frog deformities and population declines, many possible causative factors have been examined, including the input of synthetic chemicals into aquatic systems, where frogs spend much of their lives, including their entire developmental stages. Deformities in populations of green frogs in wetlands of southwestern Michigan that are influenced by agricultural, urban, or industrial inputs were assessed in this study. Of the 1445 green frogs (Rana clamitans) examined, only four (0.3%) exhibited morphological deformities. This deformity rate is less than the recognized background level of deformities for this species, which is approximately 1%. Concentrations of organochlorine insecticides, polychlorinated biphenyls (PCBs), and metals were determined in water, sediment, frog eggs, tadpoles, and adult green frog tissues. Concentrations of all individual organochlorine insecticides in tissue were less than 6 ng/g, wet wt. Concentrations of sigmaPCBs in tissue did not exceed 100 ng/g, wet wt. Concentrations of toxic metals were less than the limits of detection. Because no significant numbers of green frog deformities were observed in this region, it can be assumed that at these low concentrations, physical malformations in green frogs should not be observed. Significance of study. This study provides information on the incidence of deformities in green frog populations in southwestern Michigan and offers background data on chemical residues in green frogs and their environment.

Animals↗

Long-term assessment of insecticides treatments in West Africa: aquatic entomofauna.

For the control of the Onchocerca volvulus vector in West Africa, up to 18,000 km of rivers from 1975 and up to 50,000 km from 1989 had been partly sprayed weekly with insecticides as part of the Onchocerciasis Control Programme (OCP). To evaluate the possible short-term and long-term effects of the application of insecticides on the non-target fauna, an aquatic monitoring programme was set up during the initial phase of the programme. By analysing the invertebrate data, which were collected using various sampling strategies from four different countries between 1977 and 1996, this paper evaluates the long-term changes of the invertebrate populations with respect to their taxonomic composition as well as their trophic structures. The discussed results of the applied numerical analysis strategy suggest that neither the taxonomic nor the trophic structures are greatly altered from the range of biological, flow-related variation that normally occurs in the studied river systems. This allows us to conclude that the biological variation found here is ecologically acceptable.

Africa, Western↗

Effects of atrazine on acetylcholinesterase activity in midges (Chironomus tentans) exposed to organophosphorus insecticides.

Acetylcholinesterase activity was determined for midge larvae (Chironomus tentans) exposed to either organophosphorus insecticides (OPs) alone or OP insecticides in binary combination with atrazine (200 microg/l). Although atrazine by itself did not reduce the level of acetylcholinesterase activity, atrazine in combination with chlorpyrifos significantly decreased acetylcholinesterase activity as compared to chlorpyrifos only treatments. Although similar trends existed for malathion and methyl parathion, differences were not statistically significant. These results match previously published toxicity data where atrazine, although not acutely toxic even at much higher levels, decreased EC50 values for chlorpyrifos by a magnitude of 4, decreased methyl parathion values by a magnitude of 2, and did not decrease values for malathion.

Acetylcholinesterase↗

Relationship between biomarker activity and developmental endpoints in Chironomus riparius Meigen exposed to an organophosphate insecticide.

The biomarkers acetylcholinesterase (AChE) and glutathione S-transferase (GST) were measured in fourth-instar Chironomus riparius Meigen larvae exposed to the organophosphate insecticide pirimiphos methyl (0, 5, 10, and 50ng/g) for 48 or 96h, and at high or low food ration. Larvae exposed to 50ng/g pirimiphos methyl died within 48h. The weight of larvae exposed to 10ng/g pirimiphos methyl was significantly lower than those exposed to 0 and 5ng/g. AChE activity was significantly reduced in larvae exposed to 10ng/g, but GST activity remained unaffected. Lower food ration reduced larval weights across all treatments but did not affect biomarker measurements. Insecticide exposure was associated with a longer time to adult emergence and oviposition, fewer egg masses, a greater proportion of deformed egg masses, and fewer eggs.

Acetylcholinesterase↗

Demographic changes in Daphnia pulex (Leydig) after exposure to the insecticides spinosad and diazinon.

The toxicity of the natural insecticide spinosad was assessed against Daphnia pulex (Leydig) using a demographic approach. Data were also generated for the commonly used organophosphorus insecticide diazinon as a comparison. Exposure to spinosad led to a concentration-dependent decline in survival, birth rate (b), net reproductive rate (R(0)), and intrinsic rate of increase (r(m)). Population extinction (-r(m)) occurred after exposure to spinosad concentrations >10 microg/L for 8 days. Exposure to increasing diazinon concentrations led to an initial increase in R(0) and r(m) followed by a sharp decline, with extinction occurring after exposure to >2 microg/L after 2 days. Based on concentrations of pesticide that caused population extinction, spinosad was five times less toxic than diazinon. The stable age distribution (after 65 days) of D. pulex changed after exposure to spinosad and diazinon. Increasing concentrations of spinosad resulted in a decrease in the percentages of individuals in the first juvenile and adult stages, increase in the third and fourth juvenile stages, and little or no change in the second juvenile and adolescent stages. Diazinon had a different effect on stable age distribution. Increasing concentrations of diazinon resulted in an increase in percentages of individuals in the first and second juvenile stages, little or no change in the third and fourth juvenile stages and adolescent stage, and a decrease in the adult stage. Although spinosad and diazinon are both neurotoxins, they have different modes of action and populations of D. pulex reacted differently to each pesticide. Results of this study indicate that spinosad is significantly less toxic than diazinon to D. pulex and because it is applied at lower concentrations than diazinon it should be less hazardous to this species.

Animals↗