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Degradation of organophosphorus pesticides in soils with special reference to unaerobic soil conditions.

Organophosphorus pesticides are generally transformed by the reactions including oxidation, reduction, hydrolysis, hydroxylation, dehydrochlorination, dealkylation, methylation, isomerization, and conjugate formation. Although the degradation process of pesticides in soils is complicated, main factors may be soil constituents, soil microflora, and chemical structures of pesticides. Chemical structures are especially important for soil metabolism of organophosphorus pesticides, because the priority of the reactions mentioned above is decided. Although organophosphorus pesticides are generally hydrolyzable, the order of hydrolysis varies with chemical structures. It might be said that the slower the hydrolysis rate of the molecule, the more the possibility to be attacked by reactions other than hydrolysis. In such cases, oxidation and reduction are primarily important for the degradation of organophosphorus pesticides. Flooded soils in paddy fields give a favourable environment for the reduction of organophosphorus pesticides having labile substituents such as nitro groups. The threshold of reduction in-flooded soil is expressed as redox potential. Eh, the Eh of paddy soil fluctuates to a great extent, depending on seasons and soil types, especially organic matter content. The result of laboratory experiments with fenthion, disulfoton, Kitazin P (0,0-diisopropyl S-benzyl phosphorothiolate), edifenphos (0-ethyl S,S-diphenyl phosphorodithiolate) and amiprophos (0-ethyl 0-(2-nitro-p-tolyl) N-isopropyl phosphoramidothionate) suggested the participation of several factors mentioned above in the degradation of organophosphorus pesticides.

Anaerobiosis↗

Laboratory evaluation of five pesticides for control of Leptotrombidium fletcheri (Acari: Trombiculidae).

Five pesticides were evaluated against laboratory colonies of Leptotrombidium fletcheri (Womersly and Heaslip) by the Pasteur pipet technique. The pesticides were dieldrin (LC50 = 3.6 ppm, LC99 = 18.2 ppm), bromopropylate (LC50 = 9.2 ppm, LC99 = 239.6 ppm), dicofol (LC50 = 27.8 ppm, LC99 = 118.1 ppm), fenthion (LC50 = 15.4 ppm, LC99 = 29.7 ppm), and malathion (LC50 = 84.7 ppm, LC99 = 313.9 ppm). Dieldrin was the most toxic. Dicofol was recommended for further evaluation in field trials.

Animals↗

The neurophysiologic examination in organophosphate ester poisoning. Case report and review of the literature.

A 65-year-old woman who has been admitted after organophosphate-induced poisoning (Fenthion), develops pareses as a result of neuromuscular junctional dysfunction 7 days post-exposure. These findings are consistent with an intermediate syndrome, which may appear within 24 to 96 hours of exposure and subsides after 5 to 18 days. Delayed polyneuropathy develops within 1 to 3 weeks and abates after 6 to 12 months. A distal axonopathy can be demonstrated. Several authors have attempted EMG monitoring of pesticide-workers in agricultural and industrial settings. The electrophysiologic examination is an important diagnostic adjunct in the development and course of muscle paresis following organophosphate-ester poising.

Aged↗

Laboratory evaluation of some larvicidal agents against Anopheles culicifacies in Pune.

A laboratory study to evaluate some larvicidal agents against Anopheles culcifacies was carried out. The findings of this study brought out that the larvae of this species were highly susceptible to temephos, fenthion, Paris green and Mosquito Larvicidal Oil (MLO) in that order. The LC50 values in respect of these larvicides were 0.0009 ppm, 0.0081 ppm, 0.029 ppm and 0.015 ml respectively and LC90 values were 0.0018 ppm, 0.022 ppm, 0.11 ppm and 0.046 ml respectively.

Animals↗

Acute toxicity of mosquitocidal compounds to young mosquitofish, Gambusia affinis.

Toxicity of Florida mosquito larvicides and adulticides to 3-5 day old Gambusia affinis was determined in the laboratory. After 24-h exposure, the larvicides, temephos, fenoxycarb and petroleum distillates had LC50 values of 5.60, 1.05 and 593.4 ppm, respectively. After 24 h the adulticides resmethrin, fenthion, naled and malathion had LC50 values of 0.007, 2.94, 3.50 and 12.68 ppm, respectively. The only compound toxic to young mosquitofish at maximum field application rates was resmethrin. However, in the light of earlier tests, aerially applied adulticides generally reach the water surface at reduced concentrations and thus probably pose little or no risk to mosquitofish populations.

Animals↗

[Chronic organophosphorus intoxication and aging in rats].

Possible acceleration of aging due to the administration of organophosphorus pesticide (OP) was studied. Fenthion (6 mg/kg/day) was subcutaneously administered dorsally to rats over a period of 12 weeks. The amounts of fluorescent lipid peroxidation products (FLPP) and superoxide dismutase (SOD) activity were measured in various tissues. Microscopic examination was added only in the lens. The amount of FLPP in the retina-choroid, lens, kidney and heart of the rats was found to be increased (lens; p less than 0.01, kidney; p less than 0.05). The activity of SOD in the retina-choroid, optic nerve, liver and heart increased temporarily, but eventually returned to control levels. The lens preparations at the end of the 12-week administration period showed irregular bow configuration and epithelial nuclear dislocation in the bow area. FLPP are fluorescent products produced by peroxide lipids and their amounts increase with aging. Increase in the amounts of these products and microscopic findings for the lens were indications of the progress of aging. There is thus the possibility that the inducement of SOD production may decrease with aging. It was concluded that the organophosphorus pesticide may accelerate the aging of rats.

Aging↗

Toxicological screening for organophosphorus-induced delayed neurotoxicity: complications in toxicity testing.

The acute biocidal effects of organophosphorus pesticides are a central feature of modern agricultural chemistry, and also define the concerns of regulatory toxicology. Less well known, but more complex and idiosyncratic, is the potential for some agents to produce a delayed and progressive polyneuropathy--Organophosphorus Induced Delayed Neurotox-icity (OPIDN). On three occasions during the past ten years, the National Institute for Occupational Safety and Health (NIOSH) had been asked to evaluate human delayed neurotoxicity from three commercially available pesticides. These were leptophos, fenthion, and isofenphos. In each case, human disease was either observed or suggested by specialized toxicity testing. The reasons that federally recommended screening measures failed to identify a potential for human neurotoxicity were not accidental, but stem from a systematic approach that focuses on a traditional definition of acute lethal toxicity. The oral single dose study on one species appears to be insufficient for recognizing the delayed neurotoxic hazard of many representatives of this chemical class. The recent addition of a recommended biochemical assay--neurotoxic esterase (NTE)--to federal guidelines potentially improves sensitivity, but it is purely adjunctive and does not amend underlying ambiguities in selecting the dose and route of administration. It is also quite probable that human neurotoxicity may be a potential hazard from exposure to more than the handful of organophosphorus pesticides that have been described in the literature.

Fenthion↗

[Sensitivity of mosquito larvae to insecticides in the region of Tunis in 1984 and 1988].

Three pesticides were tested in the laboratory (Chlorpirifos, Temephos and Fenthion) against Culex pipiens larvae. The study was conducted in the Area of Tunis during the years 1984 to 1988. After several years of treatment with there organophosphoric compounds, the resistance rates reached by the treated larval population never exceeded 15, which is much lower than the rates observed in other countries.

Animals↗

Flea control on pets in southern Africa.

Aspects of the biology and life-cycle of the flea which are important to the practising veterinarian are discussed. The "cat flea", Ctenocephalides files is the most prevalent species on dogs and cats in those parts of the world where it has been surveyed. Whether the flea is a temporary or permanent obligatory parasite is still a controversy. The insecticides and product formulations available for flea control in South Africa are reviewed with emphasis on the systematic agent, fenthion. Practical protocols for flea control on dogs and cats are proposed.

Animals↗

Organophosphate resistance in Culex pipiens from Cyprus.

Populations of Culex pipiens were sampled from 8 locations in Cyprus between 1987 and 1993. All population samples generally revealed organophosphate resistance to malathion, temephos, chlorpyrifos, fenthion, dichlorvos, and pirimiphos methyl, in decreasing order of magnitude. Of 7 populations assessed with the carbamate propoxur, all proved to be resistant to different degrees. Of the 6 populations tested with permethrin, 2 were resistant to permethrin. Resistance was associated with the presence of 5 different overproduced esterases (esterases A1, A2, A5, B2, and B5) as well as an insensitive form of acetylcholinesterase. These results are discussed in relation to the ongoing mosquito abatement program in Cyprus and to similar programs in other parts of the world.

Animals↗

Organophosphate resistance in olive fruit fly, Bactrocera oleae, populations in Greece and Cyprus.

The olive fruit fly Bactrocera oleae (Gmelin) (Diptera: Tephritidae) is the most important pest of olives in countries around the Mediterranean basin. Its control has been based mostly on bait sprays with organophosphate insecticides (usually dimethoate or fenthion) for about 40 years. In the present study, the resistance status of olive fruit fly populations to dimethoate was examined in Greece and Cyprus over 2 years. Thirty-one populations from various regions of Greece, nine from Cyprus and one laboratory susceptible strain, which served as a control, were assayed by topical application of dimethoate. Considerable variation in the resistance levels to dimethoate was recorded in the populations of B. oleae, with resistance ratios ranging from 6.3 to 64.4 (ED(50) values 12.5-128.7 ng dimethoate per insect). The highest resistance ratios were found in populations from Crete, and the lowest in those from Cyprus. This variation could be attributed to different selection pressures from insecticidal applications among populations from the various regions. Migration of resistant genotypes, either autonomous or via commerce, may also be involved.

Animals↗

A convenient method for oxidation of organophosphorus pesticides in organic solvents.

Since organophosphorus pesticides can be oxidized to oxons in vivo and in the environment and their determination based on inhibition of cholinesterases can be more sensitive after their oxidation to oxons, development of an efficient method for their in vitro oxidation is important for their toxicological and analytical studies. This study demonstrated that treatment of organophosphorus pesticides with 10 molar excess bromine in acetonitrile is a rapid and efficient method for their oxidation. For the nine organophosphorus pesticides tested, the reaction was complete within a few seconds. All reactions gave the respective oxons as single major product, except that of fenthion, which gave two major products, the respective oxon and another product from further oxidation of the oxon. The yields of the oxons were 82-100%. The inhibitory power of the pesticides on acetylcholinesterase before and after oxidation was measured and, for all pesticides tested, the power after oxidation was much higher than that before oxidation. Inhibition calibration curves for both unoxidized and oxidized forms of fenitrothion and parathion were obtained. The sensitivity of the detection of these pesticides was much higher after oxidation.

Environmental Pollutants↗

Differential cytotoxic sensitivity in mouse and human cell lines exposed to organophosphate insecticides.

Neuroblastoma cell lines were used to examine the differential interspecies response (i.e., species selectivity) to organophosphates (OPs). Baseline activities of the major target esterases, i.e., cholinesterase, carboxylesterase, and neurotoxic esterase, were assayed in mouse and several human neural candidate cell lines. These activities were found to be variable within individual cell lines and among the various tested cell lines. Cytotoxicity data using the neutral red fluorometric assay were collected on both human (SH-SY5Y) and mouse (NB41A3) neuroblastoma clones exposed to a variety of OP insecticides. IC50 data indicated that the tested mouse cell line was consistently more sensitive than the human cell line to equimolar doses of various OP compounds (e.g., mipafox, parathion, paraoxon, DFP, leptophos oxon, fenthion, and fenitrothion). This difference in cytotoxic sensitivity was most pronounced in response to compounds requiring metabolic bioactivation (i.e., protoxicants). Cytotoxicity data also demonstrated that the NB41A3 mouse neuroblastoma cell line was more metabolically competent than the SH-SY5Y human cell line in converting the protoxicant parathion to its neurotoxic metabolite, paraoxon. B-lymphoblastoids, genetically engineered with human P450 cDNAs, demonstrated higher cytotoxic sensitivity to parathion than unengineered cells, indicating that cytochrome P450-associated monooxidase activity could also influence cytotoxic sensitivity to parathion in culture. These data suggest that interspecies-selectivity in response to OP-related cytotoxicity is influenced by intercellular differences in metabolism and baseline esterase activities.

Animals↗

Selective inhibitors of fatty acid amide hydrolase relative to neuropathy target esterase and acetylcholinesterase: toxicological implications.

Fatty acid amide hydrolase (FAAH) plays an important role in nerve function by regulating the action of endocannabinoids (e.g., anandamide) and hydrolyzing a sleep-inducing factor (oleamide). Several organophosphorus pesticides and related compounds are shown in this study to be more potent in vivo inhibitors of mouse brain FAAH than neuropathy target esterase (NTE), raising the question of the potential toxicological relevance of FAAH inhibition. These FAAH-selective compounds include tribufos and (R)-octylbenzodioxaphosphorin oxide with delayed neurotoxic effects in mice and hens plus several organophosphorus pesticides (e.g., fenthion) implicated as delayed neurotoxicants in humans. The search for a highly potent and selective inhibitor for FAAH relative to NTE for use as a toxicological probe culminated in the discovery that octylsulfonyl fluoride inhibits FAAH by 50% at 2 nM in vitro and 0.2 mg/kg in vivo and NTE is at least 100-fold less sensitive in each case. More generally, the studies revealed 12 selective in vitro inhibitors for FAAH (mostly octylsulfonyl and octylphosphonyl derivatives) and 9 for NTE (mostly benzodioxaphosphorin oxides and organophosphorus fluoridates). The overall in vivo findings with 16 compounds indicate the expected association of AChE inhibition with acute or cholinergic syndrome and >70% brain NTE inhibition with delayed neurotoxic action. Surprisingly, 75-99% brain FAAH inhibition does not lead to any overt neurotoxicity or change in behavior (other than potentiation of exogenous anandamide action). Thus, FAAH inhibition in mouse brain does not appear to be a primary target for organophosphorus pesticide-induced neurotoxic action (cholinergic or intermediate syndrome or delayed neurotoxicity).

Acetylcholinesterase↗

The efficacy of anthelmintics against third stage larvae of Ancylostoma caninum in Mastomys natalensis.

Investigations have been carried out on the multimammate rat (Mastomys natalensis), orally infected with 1000 third stage larvae of Ancylostoma caninum per animal, to evaluate the larvicidal efficacy of anthelmintics in this paratenic host. The oral or subcutaneous administration of 19 anthelmintics and filaricides revealed good activity for levamisole, cambendazole, and mebendazole against 15-day-old Ancylostoma larvae which were located in the muscular tissue. Similarly, good results were obtained with levamisole and cambendazole against the migrating third stage larvae, by treatment two to six days after infection. The benzimidazole derivatives, thiabendazole, oxibendazole, parbendazole, and fenbendazole showed marked activity only at high dosage rates. The anthelmintics methyridine, amoscanate, pyrantel tartrate, morantel tartrate; the microfilaricidal organophosphates dichlorvos, fenthion, and haloxon; as well as the micro- or macrofilaricidal drugs diethylcarbamazine, nitrofurantoin, nifurtimox, suramin sodium, and thiacetarsamide sodium failed to show larvicidal activity even in high dosages. The average larval recovery rate after oral infection with 1000 third stage larvae, in untreated control animals, was 14.85%.

Ancylostoma↗

Validation of an SPME method, using PDMS, PA, PDMS-DVB, and CW-DVB SPME fiber coatings, for analysis of organophosphorus insecticides in natural waters.

Solid-phase microextraction (SPME) has been optimized and applied to the determination of the organophosphorus insecticides diazinon, dichlofenthion, parathion methyl, malathion, fenitrothion, fenthion, parathion ethyl, bromophos methyl, bromophos ethyl, and ethion in natural waters. Four types of SPME fiber coated with different stationary phases (PDMS, PA, PDMS-DVB, and CW-DVB) were used to examine their extraction efficiencies for the compounds tested. Conditions that might affect the SPME procedure, such as extraction time and salt content, were investigated to determine the analytical performance of these fiber coatings for organophosphorus insecticides. The optimized procedure was applied to natural waters - tap, sea, river, and lake water - spiked in the concentration range 0.5 to 50 micro g L(-1) to obtain the analytical characteristics. Recoveries were relatively high - >80% for all types of aqueous sample matrix - and the calibration plots were reproducible and linear (R(2)>0.982) for all analytes with all the fibers tested. The limits of detection ranged from 2 to 90 ng L(-1), depending on the detector and the compound investigated, with relative standard deviations in the range 3-15% at all the concentration levels tested. The SPME partition coefficients (K(f)) of the organophosphorus insecticides were calculated experimentally for all the polymer coatings. The effect of organic matter such as humic acids on extraction efficiency was also studied. The analytical performance of the SPME procedure using all the fibers in the tested natural waters proved effective for the compounds.

Acrylic Resins↗

Determination of organophosphorus insecticides in natural waters using SPE-disks and SPME followed by GC/FTD and GC/MS.

Two methods for the analysis of ten organophosphorus insecticides in natural waters using solid phase extraction disks containing C18 and SDB and solid phase microextraction fibers containing polyacrylate (PA) are developed. Bromophos ethyl, bromophos methyl, dichlofenthion, ethion, fenamiphos, fenitrothion, fenthion, malathion, parathion ethyl and parathion methyl were determined by GC/MS and GC/FTD. The SPE-disks require only 1000 mL of sample and provide a method limit of detection in the range of 0.01-0.07 microgram/L and recovery rates from 60.7 to 104.1%. The solid phase microextraction (SPME) technique requires 2-5 mL of water sample and provides a method limit of detection in the range of 0.01 to 0.05 microgram/L for all detectors and the recoveries compared to distilled water ranged from 86.2 to 119.7%. The proposed methods were applied to the trace level screening determination of insecticides in river water samples originating from different Greek regions.

Calibration↗

Avian mortality events in the United States caused by anticholinesterase pesticides: a retrospective summary of National Wildlife Health Center records from 1980 to 2000.

We reviewed the U.S. Geological Survey National Wildlife Health Center (NWHC) mortality database from 1980 to 2000 to identify cases of poisoning caused by organophosphorus and carbamate pesticides. From the 35,022 cases from which one or more avian carcasses were submitted to the NWHC for necropsy, we identified 335 mortality events attributed to anticholinesterase poisoning, 119 of which have been included in earlier reports. Poisoning events were classified as confirmed (n = 205) when supported by findings of > or =50% inhibition of cholinesterase (ChE) activity in brain tissue and the detection of a specific pesticide in the gastrointestinal contents of one or more carcasses. Suspected poisonings (n = 130) were defined as cases where brain ChE activity was > or =50% inhibited or a specific pesticide was identified in gastrointestinal contents. The 335 avian mortality events occurred in 42 states. Washington, Virginia, and Ohio had the highest frequency of events, with 24 (7.2%), 21 (6.3%), and 20 (6.0%) events, respectively. A total of 8877 carcasses of 103 avian species in 12 orders was recovered. Because carcass counts underestimate total mortality, this represents the minimum actual mortality. Of 24 different pesticides identified, the most frequent were famphur (n = 59: 18%), carbofuran (n = 52; 15%), diazinon (n = 40; 12%), and fenthion (n = 17; 5.1%). Falconiformes were reported killed most frequently (49% of all die-offs) but Anseriformes were found dead in the greatest numbers (64% of 8877 found dead). The majority of birds reported killed by famphur were Passeriformes and Falconiformes, with the latter found dead in 90% of famphur-related poisoning events. Carbofuran and famphur were involved in mortality of the greatest variety of species (45 and 33, respectively). Most of the mortality events caused by diazinon involved waterfowl.

Acetylcholinesterase↗