Systemic pesticides carbamates

With an excessive, single exposure, the result will be either a systemic pesticide poisoning or a topical lesion frequently observed on the skin or in the eyes. Since most acute intoxications are from the carbamate and organoposphate insecticides, the systemic manifestations are cholinergic and are due to the inhibition of acetyl cholinesterase and the resultant accumulation of the neurotransmitter acetylcholine, at the synapse. Topical effects, in contrast, either are the result of the irritant properties of the chemicals in the formulation or have an allergenic basis for their occurrence (3). However, topical effects are not necessarily exclusively the result of exposure to the active ingredient in the formulation but may result from a reaction to one or more inerts as well. 

Pesticide Solvent. The majority of organic fungicides, insecticides, and herbicides (qv) are soluble in DMSO, including such difficult-to-solvate materials as the substituted ureas and carbamates (see Fungicides, agricultural Insect control technology Pesticides). Dimethyl sulfoxide forms cosolvent systems of enhanced solubiUty properties with many solvents (109). 

L. Pogacnik and M. Franko, Optimisation of FIA system for detection of organophosphorus and carbamate pesticides based on cholinesterase inhibition. Talanta 54, 631-641 (2001). 

The above-mentioned system has also been used for the indirect CL determination of some carbamate and organophosphorous pesticides that inhibit acetylcholinesterase. Acetylcholinesterase in solution or immobilized on methacrylate beads is coupled to immobilized choline oxidase and peroxidase [46],... 

Pharmacologically, carbofuran inhibits cholinesterase, resulting in stimulation of the central, parasympathetic, and somatic motor systems. Sensitive biochemical tests have been developed to measure cholinesterase inhibition in avian and mammalian brain and plasma samples and are useful in the forensic assessment of carbamate exposure in human and wildlife pesticide incidents (Bal-lantyne and Marrs Hunt and Hooper 1993). Acute toxic clinical effects resulting from carbofuran exposure in animals and humans appear to be completely reversible and have been successfully treated with atropine sulfate. However, treatment should occur as soon as possible after exposure because acute carbofuran toxicosis can be fatal younger age groups of various species are more susceptible than adults (Finlayson et al. 1979). Carbofuran labels indicate that application is forbidden to streams, lakes, or ponds. In addition, manufacturers have stated that carbofuran is poisonous if swallowed, inhaled, or absorbed through the skin. Users are cautioned not to breathe carbofuran dust, fumes, or spray mist and treated areas should be avoided for at least 2 days (Anonymous 1971). Three points are emphasized at this juncture. First, some carbofuran degradation... 

Potential Uses of These Polymers. We have studied the phenyl isocyanate modification of poly(vinyl alcohol) as a model system. Many uses exist for carbamates as medicines, pesticides and herbicides (67,68). For example, ethyl carbamate has been used to treat leukemia and multiple myeloma. Ethyl carbamate has also been used as an antidote for central nervous system poisoning by strychnine. The tranquilizer Meprobamate is a carbamate derivitive. Numerous pesticides and herbicides, such as Sevin and Propham, are also carbamate derivatives. Propham is isopropyl N-phenylcarbamate which bears a strong resemblence to the polymers of Equation 21, and this compound is used as a preemergence herbicide. Numerous other close analogs could be cited also. We might note also that the N-phenyl carbamoyl unit bears... 

Studies were initiated at Iowa State University in 1977 to determine if pesticides would be contained and degraded when deposited in water/soil systems. Although the addition of known amounts of the selected pesticides was controlled, the physical environment was not temperature, humidity, wind speed, etc. were normal for the climate of Central Iowa. Four herbicides and two insecticides were chosen on the basis of three factors. Firstly, they represented six different families of pesticides. The four herbicides, alachlor, atrazine, trifluralin, and 2,4-D ester, represent the acetanilides, triazines, dinitroanilines, and phenoxy acid herbicides, respectively. The two insecticides, carbaryl and para-thion, represent the carbamate and organophosphorus insecticides, respectively. Secondly, the pesticides were chosen on the basis of current and projected use in Iowa Q) and the Midwest. Thirdly, the chosen pesticides were ones for which analytical methodology was available. 

Organophosphate and carbamate cholinesterase inhibitors (see Chapter 7) are widely used to kill insects and other pests. Most cases of serious organophosphate or carbamate poisoning result from intentional ingestion by a suicidal person, but poisoning has also occurred at work (pesticide application or packaging) or, rarely, as a result of food contamination or terrorist attack (eg, release of the chemical warfare nerve agent sarin in the Tokyo subway system in 1995). 

The carbamate pesticides can also be determined by normal-phase chromatography on different columns. Silica (113-116), amine (51), and cyanopropyl (112) columns have been used for the determination of carbamate residues. These columns were used with different solvent systems, with isopropanol-heptane being the mobile phase producing generally better results and methylene chloride-heptane the preferred solvent system when nonpolar carbamates were present in the sample. Another mobile phase used was iso-octane-dioxane (113). Although normal-phase mode was for the most part satisfactory, reversed-phase mode gave generally superior results. 

MT Tena, MD Luque de Castro, M Valcarcel. Total and individual determination of carbamate pesticides by use of an integrated flow-injection/HPLC system. J Chromatogr 33 449-453, 1992. 

Method 1 (cellulose layers). The cellulose powder is washed twice with isopropanol-ammonium hydroxide-water (6 3 1), washed once in isopropanol and dried at 10S °C for 8 h. The plates (thickness, 0.25 mm) are prepared with a commercial TLC applicator. The slurry consists of 15 g of prepared cellulose in 85 ml of water which has been homogenized in a blender. The plates are dried at room temperature, and then eluted with diethyl ether in order to remove organic impurities. The plates are dried in air immediately before use. The pesticides are spotted and developed with appropriate solvent systems. The chromatoplate is dried in air and sprayed lightly with a 0.05% solution of fisetin in isopropanol. The separated spots are observed visually under a UV light at 365 nm (excitation, 370 nm emission, 533 nm). This method has been examined for several types of pesticides including carbamates, organophosphates, triazines and chlorinated hydrocarbons. 

The use of NBD-Cl for the fluorescence analysis of alkylamine-generating pesticides has been investigated [173]. A two-phase reaction system is employed for the hydrolysis and labeling of N-methyl- and N,N-dimethyl-carbamate pesticides. The residue is hydrolyzed in 0.1 M sodium carbonate and the liberated amine is treated with NBD-Cl in an organic phase (IBMK, isobutyl methyl ketone) above the aqueous layer. An aliquot portion of the organic layer is used for chromatography. The reactions involved are shown in Fig. 4.65. 

The Department has developed methods for monitoring the exposure of workers exposed to organophosphate and carbamate pesticides. These methods utilize the determination of plasma and red blood cell cholinesterase activities and urinary alkyl phosphates. Studies are reported vrti ich show that these methods have proven useful in evaluating the safety effectiveness of closed-transfer systems and in determining reentry times for field workers. 

Acetylcholine is a neurotransmitter that functions in conveying nerve impulses across synaptic clefts within the central and autonomic nervous systems and at junctures of nerves and muscles. Following transmission of an impulse across the synapse by the release of acetylcholine, acetylcholinesterase is released into the synaptic cleft. This enzyme hydrolyzes acetylcholine to choline and acetate and transmission of the nerve impulse is terminated. The inhibition of acetylcholineasterase results in prolonged, uncoordinated nerve or muscle stimulation. Organophosphorus and carbamate pesticides (Chapter 5) along with some nerve gases (i.e., sarin) elicit toxicity via this mechanism. 

Evidence was obtained recently that pesticide vapors may enter the air by still another mechanism, involving plant circulation and water loss (57). Rice plants were found to efficiently transport root-zone applied systemic carbamate insecticides via xylem flow to the leaves, eventually to the leaf surface by the processes of guttation and/or stomatal transpiration, and finally to the air by surface volatilization. Results from a model chamber showed that 4.2, 5.8, and 5.7% of the residues of carbaryl, carbofuran, and aldicarb, respectively, present in rice plants after root soaking vaporized within 10 days after treatment. The major process was evaporation of surface residues deposited by guttation fluid. 

The remainder of this paper will describe specific applications of FTIR in support of one of Diamond Shamrock s pesticide programs. All the results described here were obtained from studies of a single compound, thiofanox (P), 3,3-dimethy1-1-methylthio-2-butanone 0-[(methylamino)carbonyl]oxime. Thiofanox is a potent systemic and contact carbamate insecticide. The infrared spectrum of thiofanox is shown in Figure 4. The major peaks in the spectrum are the N-H stretch at 3380 cm-1,... 

Carbamates also include pesticides such as Sevin, aldicarb, and carbaryl. They are more degradable than organophosphates and have lower dermal toxicides. Their toxicity is also due to inhibition of acetylcholinesterase but they do not penetrate the central nervous system, so most effects are respiratory in nature. An acetylcholinesterase, which has been carbamylated can undergo spontaneous hydrolysis in vivo, which reactivates the enzyme leading to less severe symptoms or a shorter duration of symptoms. Carbaryl has a low toxicity for mammals however, Perimicarb is highly toxic to mammals, but not readily absorbed through the skin. 

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