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6.2
1. Poisons: any agent capable of producing a deleterious response in a biological system, seriously injuring function or producing death. 2. All Substances are Poisons: there is none which is not a poison. The right dose differentiates a poison and a remedy (Paracelsus 1493-1541). Fine line between a poison and medicine. 1
Any chemical substance may evoke one or both of two toxic effects. They are the acute toxic effect and the chronic toxic effect. 6.2.1 Acute Toxic Effect This is the one more readily comprehensible to the layman, and normally occurs shortly after contact with one single dose of poison. The magnitude of the effect depends on the innate toxicity of the substance and upon its method of application to a particular organism. 6.2.2 Chronic Toxic Effect This occurs when an organism is exposed to repeated small and non-lethal doses of potentially harmful substance. Well-known chronic responses to various instants include long cancer, brain damage and necrosis of the liver and kidneys. Table 1. Acute toxicity of insecticides and other substances.
COMPOUND Botulinus toxin A aldicarb (temic) disulfoton (Disyston) parathion strychnine Mercury nicotine dichlorvos propoxur DDT ACUTE ORAL TOXICITY LD50 (mg/kg) 0.0014 0.9 4.5 8.3 30 37 55 68 90 113 COMPOUND rotenone gasoline warfarin caffeine demethoate (Cygon) diazinon chlordane 300 382 500 820 1200 1375 3300 3500 4240 4500 none ACUTE ORAL TOXICITY LD50 (mg/kg) 132 150 186 200 215
FREQUENCE OF EXPOSURE
or e xc re t io n
Acute Dose
-n
et
ab
oli
sm
Ch r
on
ic
Do s
Residual injury
NOEL:
Figure 1. Diagrammatic view of dose and corresponding measure of effect. Acute dose is compared to the cumulative dose after multiple administration of a chemical that has limited elimination and
thus accumulates, and one that produces injury, which accumulates with multiple dosing (Klassen et al. 1986). 6.2.3 Measure of Toxicity A frequently used measure of acute toxicity is the 50% lethal dose or LD50. It is the amount of poison, which kills half the organisms in a randomly chosen batch of a named species when applied in a particular way under stated experimental conditions. It is usually expressed in terms of milligram poison per kilogram body weight of the experimental organism. This LC50 is a somewhat similar concept to the LD50. It is the concentration, usually in the air or water surrounding experimental animals, which causes 50 percent mortality. To determine the LD50 of a substance, batches of animals are exposed to a range of doses and the percentage of organisms dying in each batch is recorded. The results can usually be represented by the (idealized) sigmoid curve shown in Figure 6.2.3. It should be noted that compounds with smaller LD50 s are more toxic than the compounds with large LD50 s, and that mg/kg or ( g/g) is equivalent to expressing a toxic dose as parts per million body weight. 100
Percentage kill
50 0 Log LD50 (=m) Increasing log concentration 3
Fig.6.2.3 The relationship between Increasing log concentration and Percentage kill
(term not being bearing the suffix-cide) Anti-feedant.. inhibits feeding while insects remain on the treated plants; the insects eventually starve to death. Anti-transpirant. reduce transpiration Attractant.. lures pests to treated location, eg. sex attractants. Chemosterilant.. destroys a pests ability to reproduce Defoliant.. removes unwanted plant growth without immediately killing the whole plant Desiccant.. dries up plant parts and insects Disinfectant ..destroys or inactivates harmful organisms Feeding stimulant.. causes insects to feed more vigorously Growth regulator. stops, speeds up or retard growth processes of plants or insects. Repellent. drives pests away from treated object without killing them. Semiochemicals.. pheromones, allomones and kairomones; substances emitted by plants or animals, which stimulate or inhibit certain behavioural activities of insects. Synergist.. enhances the effectiveness of an active agent.
Insecticides may also be classified according to the various ways they enter or affect pests. Once on or inside a pest organism, an insecticide may act upon one or more of the life processes. The result may be death, illness or a change in the behaviour, growth, metabolism or reproductive capabilities of the pest. The following are some examples of their method of classification. 1. Stomach toxicants generally enter a pests body through the mouth during feeding (ingestion) and are absorbed through the digestive tract. 2. Contact toxicants generally penetrate a pests body as a result of contact with the legs or other external portions and treated surfaces such sprayed leaves. 3. Fumigants are volatile and enter a pests body through the respiratory system and kill at lethal concentration. 5
4. Systemic toxicants are characterized by high water solubility, by which property they can readily be taken into the plant through its roots, stems or leaves. Once inside the plant, systemic insecticides move through the plants vascular to other untreated parts from were insects acquire the translocated insecticide during feeding. Systemic insecticides are particularly effective against sucking, boring and mining insects and nematodes and are also used to control pests of livestock. 5. Suffocating materials, usually oils, clog the respiratory mechanism of pests, isomerism.
Inorganic compounds
are derived from naturally occurring elements and do not contain carbon. They are stable, non-volatile chemicals frequently soluble in water. Many of them are persistent; those containing arsenic, cyanide, mercury and thallium are cumulative poisons. Because of their residual persistence and high mammalian toxicity, the use of almost all inorganic chemicals has been discontinued in favour of lees hazardous synthetic organic ones. Examples of inorganic chemicals are: boric acid copper hydroxide copper oxychloride copper sulphate sodium arsenite sodium chlorate sodium fluoride sodium fluoroacetate mericuric oxide mercurous fluoaluminate (cryolite) thallium sulphate The elements copper and sulphur formulated as dusts or sprays are still widely used as fungicides (see below). Cryolite is regaining a place as a selective insecticide in integrated pest control. Boric acid and silica gels affect the waxes of an insects cuticle, which becomes permeable to water from the insects body. Consequently, the insect dies from dehydration. Both boric acid and silica gels are used in baits for controlling household insects such as cockroaches and ants. 6
6.4.2.3 Botanicals
Botanicals, also known as natural insecticides, are toxicants that have been derived from plant materials. These may be produced in the form of powder made from finely ground plant parts or extracts, which are used in sprays. Neem extracts obtained from the neem tree (Azadirachta indica) have an insecticidal, repellent, anti-feedant and growth inhibiting effect on many insects belonging to six taxonomic orders. Neem seed oil, admixed at 3-5 ppm concentration, protects stored beans against bruchid bean beetles for a period of up to six months. Watery extracts from neem leaves and fruit can be sprayed at weekly intervals against leaf-feeding caterpillars on vegetables. Neem is nonhazardous to man and other mammals, and there are no harmful side-effects on natural enemies. Nicotine is an alkaloid extracted from tobacco leaves (Nicotiana tabacum) that has long been used as an insecticide, but since it is also a strong neuromuscular poison in man and animals, its use is discouraged. Pyrethrum is extracted from chrysanthemum flowers. (C.cinerariaefolium). Pyrethrum is a powerful degradable contact insecticide causing a rapid knockdown action, but insects may recover. Insecticidal activity is markedly increased by the addition of synergists, eg. piperonyl butoxide. Pyrethrum is very safe to man and mammals. As dusts or sprays, pyrethrum is used in animal husbandry, in stored food protection and in households. Scilliroside is a very toxic glucoside with stomach action, which is extracted from ground bulbs of the red squill, Urginea (Scilla) maritime. Mixed with bait, it controls most species of rats and mice. Rotenone is extracted from the roots of bean legumes, i.e Derris spp. in South-east Asia and Lonchocarpus spp. in South America. It has long been used as an insecticide and is still used as a pesticide. Because of its toxicity to fish and its relatively short residual effect, it can be employed in fish farming to clean unwanted fish from ponds prior to restocking. Ryania is obtained from the stem of Ryania speciosa, a shrub from South America. It has a high mammalian toxicity with symptoms resembling these evolved by strychnine, an intense mammalian poison extracted from Strychnos spp. seeds. Its use should be discouraged. Sabadilla is an alkaloid extracted from seeds of Schoenocaulon officinale (Liliaceae). It too is a superseded compound. 7
3. They comprise a notorious group of insecticides, among which are DDT and BHC; both these of were synthesized more than hundred years ago. 4. However, it was only around 1940 that their insecticidal properties were recognized. This event gave birth to era of synthetic organic pesticide manufacture. DDT become famous for its efficacy against flies, mosquitoes, body lice and bubonic plague. DDT was also used on a large scale in agriculture and horticulture. Because of its low cost, it compounds may be distinguished: 6.4.3.1 Diphenyl aliphatics Chlorobenside DDT chlorofenethol dicofol Although DDT has a high oral LD 50 value than the organo phosphates, it has a long residual life or persistence in the soil in aquatic environments. Also, because it accumulates in the tissues of animals and plants, it is banned for agricultural use. However, its use continues in health programmes for mosquito control. The other five compounds are very effective miticides, and do not have the long persistency of DDT. 6.4.3.2 Benzene derivatives benezene hexachloride (BHC, HCH) lindane (Gemma BHC) pentachlorophenol
BHC is a chlorinated benzene consisting of a mixture if five isomeres, of which only the Gamma isomer was found to have insecticidal properties; the other four being insecticidally inactive ingredients. A product containing 99% Gammaisomer, namely lindane, is highly effective, but too expensive for large-scale crop use. The four inert isomers have a musty flavour that persist in animal and plant tissues as well as in the soil. Hence, normal mixture BHC, containing only 12% Gamma-isomer, affects the taste of rot crops and vegetables. Because the Gamma-isomer is odorless, lindane was previously widely used in the control of storage pests. HCH (BHC) cl cl cl
cl
cl
cl 1,2,3,4,5,-hexachlorocyclohexane 6.4.3.3 Cyclodienes endrin heptachlor endosulfan Generally, cyclodienes are persistent soil insecticides, mainly used against coleopterous insects and termites; they also are generally photostable. Used of cyclodienes is progressively being cancelled or banned (aldrin and dieldrin) for reasons of resistance in insects, fish toxicity and serious environmental hazard. In Western countries, only endosulfan is still registered for use on field crops.
Cl Cl
O
ENDOSULFAN
S
O
Cl2 Cl Cl
6.4.3.4 Polychloroterpenses Camphechlor (Toxaphene) For 25 years until 1980, Toxaphene had the greatest use of any single insecticide in agriculture. In cotton cultivation, it was widely used in mixtures initially with DDT and later with methyl parathion. Although Toxaphene is persistent in the soil, it evaporates from plant surfaces within weeks. It has low mammlian toxicity, but is toxic to fish.
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O 0,0-dimethyl-S-1,2 di (carboethoxy) ethy phosphorodithioate. Naled is another safe OP-compound having a very short residual action and a fumigant quality. As is the case malathion, it is widely used for the control of mosquitoes, flies and ecto-parasites of domestic animals. Several aliphatic OPs, such as monocrotophos, demeton and dimethoate, have a systemic action. These compounds are particularly effective against sucking insects. Some aliphatic OP-insecticides-although being highly toxic-have such very short residual activity that they are preferred for use on vegetables. Examples are listed hereunder (i) methamidophos (ii) mevinphos (iii) monocrotophos (This insecticide is now banned in many countries including SriLanka) (iv) malathion 6.3.4.2 Phenyl Organophosphates These compounds are generally more stable than aliphatic ones and more persistent. Parathion-ethyl was introduced in 1947; with widespread use, it came to be known as parathion. Because of its dangerously high toxicity, it has largely be replaced by the slightly less and broad acting parathion-methyl. Several older members of this class, such S (CH3O)2 P O 11
METHYL PARATHION
NO2
0,0-dimethyl 0-p-nitrophenyl phosphorothioate as fenitrothion and tetrachlorvinphos, are widely used in agriculture, horticulture and public health programmes. Examples in this group are: (i) parathion (iv) fenitrothion (ii) parathion-methyl (v) fenthion (iii) chlorfenvinphos
6.4.4.3 Heterocyclic organophosphates Heterocyclic compounds have complicated molecular structure and are generally longer lasting than most of the aliphatic and phenyl derivatives. Upon degradation they may break down into many metabolities which may be difficult to analyse, some are very effective against mites and soil insects. Examples of this group are: (i) chlorpyrifos (ii) chlorpyrifos-methyl (v) quinalphos (vi) pirimiphos-methyl (iii) phosmet (iv)diazinon
PIRIMIPHOS-METHYL
CH3
N(CH2CH3)2
P S
(OCH3)2
0-[2 (diethylamino)-6-methyl-4-pyrimidinyl] 0,0-dimethylphosporothioate Organo-sulphur compounds contain a dominant sulphur atom and commonly two phenyl rings. Sulphur alone has a good efficacy against mites but, in combination with the two phenyl rings, its acaricidal or miticidal effect is enormously enhanced. Organosuphurs combine this high toxicity to mites with a remarkably low toxicity to insects; thus, they are very selective miticides and useful in integrated pest management. Examples of this group are: (i) ovex (ii) propargite (iii) tetradifon
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6.4.5 Carbamates
These compounds resemble closely the organophosphates in biological activity and, like them, they CARBARYL O O C N H CH3
1-napthyhl N-methylcarbamate O OH C N H 1. Carbamates are esters of carbamic acid 2. Inhibit the cholinesterase enzyme required for nerve function in animals. 3. They generally have a short residual activity and a very broad-spectrum effectivity as insecticides, miticides, nematicidies and molluscicides. 4. The carbamate group also includes herbicides such as diallate and propham. (The groups of thiocarbamates and dithiocarbamates are considered under herbicides and fungicides, respectively.) Among the carmamates, three classes of compounds may be distinguished: 6.4.5. Methyl carbamates with Phenyl ring structure (i) aminocarb (ii) BPMC (iii) carbaryl (v) isoprocarb (MICP) (vi)propoxur (iv) promecarb H CARBAMIC ACID
Carbaryl has become very popular in horticulture because of its low toxicity and broad spectrum efficacy. The carbamates propoxur, bendiocarb and dioxacarb are used to control mosquitoes, household and storage pests because of their rapid knockdown effect and long residual efficacy in wall surfaces. CH3 6.4.5.1 Carbofuran CH3 O O C O NH 13 CH3
2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate
dimethyl
carbamates
with
6.3.5.3 Methyl carbamates of oximes having a chain structure (i) aldicarb (ii) oxamyl (iii) methomyl ALDICARB CH3 CH3 S CCH CH3 N O CH3 O C NH (iv) thiodicarb
2-methyl-2-(methylthio)propionaldehyde 0-(methylcarbamoyl) oxime Thiodicarb is relatively new compound with a double carbamate molecule linked with a sulphur atom; it has a long residual activity of up to 14 days. 6.3.6 PYRETHROIDS Pyrethroids are synthetic compounds, the chemical structure of which is patterned after pyrethrins (extracted from the chrysanthemum flower), a mixture if six esters named cinerin I and II, jasmolin I and II and pyrethrin I and 14
II. The synthetic pyrethroids mimic the broad efficacy of the botanical,, but, as they contain only one of these esters, insect species tend to develop resistance to them. Compared with the botanical pyrethrum, which contains all six ester properties, no resistance has yet been observed as it becomes very difficult for insects to develop the requisite combination of alternative pathways to these six properties. Generally, pyrethroids show low mammalian toxicity, but like pyrethrum, they are highly toxic to fish and bees. They are anoxic nerve poisons. Their residues in crops do not cause problems. The mode of action of pyrethroids resembles organochlorines. Pyrethrum and the older the synthetic pyrethroids are very sensitive to sunlight, because their molecules split under ultra-violet light. Therefore, they are not suited to agricultural use, but some of them have good volatility and are very effective against indoor insect pests. For household use they are formulated as aerosols together with piperonyl butoxide for synergistic action. Examples are: (i) allethrin resmethrin (v) bioresmethrin (ii) Phenothrin (iii) bioallethrin (vi) tetramethrin (iv)
From the early 1970s, pyrethroids have been produced which have better photo-stability with low volatility; therefore, they may be used for agricultural purposes. Examples are: deltamethrin permethrin fenvalerate The latest groups of synthetic pyrethroids are photo-stable as well as extremely toxic insects. Their efficacy is so good that a dose of only 10-40 g active ingredient per hectare is required. These new pyrethroids are not mixed with synergists. Examples are: (i) bifenthin (ii) fenpropathrin (iii) cyfluthrin (iv) fluvalinate (v) cypermethrin (vi) tralomethrin
FENPROPATHRIN
(CH3)2
O C O
C CH
N O
15
Diflubenzuron
16
Figure 1. Chemical structures of various benzophenyl urea analogues with insecticidal activity. 2. Studies on the mode of action of diflubenzuron revealed that the compound alters cuticle composition - especially that of chitin - thereby affecting the elasticity and firmness of the endocuticle. The reduced level of chitin in the cuticle seems to result from inhibition of biochemical processes leading to chitin formation. Chitin is a polysaccharide made up of N-acetyl-Dglucosamine and glucosamine units linked through b-1,4-glucosidic bonds. Initial research into the mode of action of benzophenyl ureas indicate that they act to inhibit chitin biosynthesis. Chitin formation is dependent upon the formation of a high energy intermediate UDP-acetylglucosamine complex which is formed at the expense of UTP. The enzyme chitin synthetase, is responsible for the transfer of an N-acetylglucosamine unit from this complex to a pre-existing poly(N-acetylglucosamine) primer. It has been clearly established that benzophenylureas (BPU) act to inhibit chitin formation, but the precise molecular site of this inhibition remains uncertain. One possible explanation is that they act as inhibitors of chitin synthetase, although in vitro inhibition of the enzyme has not been demonstrated. Others have suggested that BPU's prevent activation of a precursor of chitin synthetase from a precursor molecule. Another suggestion is that activated metabolites or formed within the body but thus far none have been identified. It is of interest that chitin synthetase systems in fungi are not sensitive to BPU's; this appears to imply that the primary target of these substances is some reaction or control mechanism of particular relevance to insects. 3. The biochemical effects of benzophenylureas on chitin synthesis directly affect the insect's maulting physiology. The spectrum of effects of BPU's reflects this primary mode of action. The effects may be categorized as follows: 1. Disruption of ecdysis. After exposure to BPU's, symptoms are generally not observed until the maulting process is initiated. Apolysis is completed normally, however, ecdysis is disrupted. Severity of ecdysis disruption is related to dosage and nature of the BPU.
2. Failure to feed. With a number of insects exposed to BPU's, maulting appears normal, but the mandibles and labrum may be displaced such that the insect is not able to feed In addition to selectivity resulting from a mode of action that is specific to insects, benzophenyl ureas affect larval stages of pest insects that are actively synthesizing chitin. Therefore, the effects on adults of non-target species, e.g. parasites, predators and pollinators are minimized. The 17
compounds are effective mainly by ingestion, but in some species, suppression of fecundity and ovicidal activity have been demonstrated. In addition, because of the novel target site, these compounds are less likely to be affected by resistance mechanisms common to more traditional insecticides.
Phenoxyphenoxy carbamate
Figure 2. Some of the major juvenile hormone analoguesues of commercial importance. The use of the natural juvenile hormone as a selective insecticide is not feasible because of its environmental instability and difficulties of synthesis. The major breakthrough came when in was observed that 18
synthesized aromatic terpenoid ethers were several hundred-fold more active than the natural hormone. Juvenile hormone analoguess functionally resemble JH, and may or may not be similar in structure. The lipophilic nature of JH allows use of structural analogues as pesticides since it can penetrate the insect cuticle. 2. The effects of juvenile hormone analogues are complex, and vary from one analogues to another, and can act either as JH agonist or antagonists or a mixture of both. The natural hormone has two distinct effects: one during the larval stage and the other in the adult. During the larval stage it suppresses metamorphic change during molting, and in the adult, it induces vitellogenin synthesis during ovarian development. Since JH is a hormone, the regulation of secretion, transport, degradation, excretion and feedback control are all important biochemical mechanisms with which an analogues might interfere. The presence of JH must be precisely timed in order for to exert juvenilizing activity at the appropriate stage in development. Removal and degradation of JH is accomplished by specific esterases. Many of the analogues escape the normal degradation route of the natural hormone and exert an agonistic function as well as stimulate production of JH esterases such that degradation of the natural hormone is enhanced. Inhibition of JH esterases by the analogues would also disrupt the regulatory mechanisms responsible for JH removal. JH analogues may also interfere with activities of other hormones. Methoprene has been shown to inhibit the release of prothoracicotropic hormone, which in turn prevents the secretion of ecdysone. 2. The physiological effect of JH analoguess are seen mainly during the larval-pupal transformation. The action of these compounds produces various degrees of incomplete metamorphosis or production of supernumerary instars (i.e. extra instars in insects that should have molted to pupae or adults).
2. Although the JH mimics clearly demonstrate the relative safety, selectivity, and efficacy that endocrine-based insecticides will possess, their effectiveness is limited to pests that cause damage to adults such as flies and mosquitoes, or for insects that take many genrations to build up damaging populations, such as aphids and scales.
1. Precocenes: These compounds are plant derived from the bedding plant (Ageratum houstonianum) and observed to have anti JH activity. Because these compounds induced precocious development they were named precocenes.
Figure 3. Precocene
The mechanism of precocene is unique since it is a selective cytotoxin for the active corpus allatum. Precocene treatment results in progressive degeneration of the corpus allatum. The epoxidase enzyme necessary for the synthesis of juvenile hormone is also responsible for the metabolism of precocene in the corpus allatum. This enzyme reacts with precocene and forms a transient but reactive epoxide which alkylates the proteins in the corpus allatum causing cellular death. In addition to inducing precocious development in young nymphs, precocene has been shown to prevent ovarian development, induce atrophy of corpora allata, and inhibit in vitro biosynthesis of juvenile hormone by corpora allata. Unfortunately, precocene is generally active only on some heteroptera and some grasshoppers only at extremely high doses. The lack of activity against most holometabola, and the high dosage required for its effect on others, have limited the marketability of these compounds.
6.7.3.3 Formamidines
1. The two commonest members of this group are chlordimeform and amitraz. These compounds are characterized by their ability to evoke a variety of behavioral and other effects in a limited range of insects and more importantly, certain mites and ticks.
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Figure 4. The structures of two formamidines. The broken lines indicate common loci for metabolism 2. These compounds are included with the endocrine-based insecticides since their mode of action involves activity at receptors of the biogenic amines, specifically at octopamine receptors. Biogenic amines in insects are though to act as neuromodulators that are released by neurons and modulate the reaction of another transmitter with its receptor. Octopamine has received the most attention as a neuromodulator in insects and it is believed to function similarly to adrenaline in vertebrates (i.e. produces characteristic "fight or flight" symptoms).
3. The effects of formamidines are diverse. They have been described as having a repellent action, yet an affected organism will not feed even if provided with insecticide-free food. Organisms can suffer an increase excitability leading to ineffectual probing of the food source, attempts to fly or aimless walking. Disruption of behavioral patterns essential to mating and reproduction are also common. 4. The generally accepted target site for formamidine insecticides is the octopamine receptor. Some author's report that these compounds occupy the octapamine receptor in a way that leads to an agonistic response (i.e. the occupation leads, not to a blocking of octopamine activity, but to sustained and abnormal octopamine-like stimulation).
Others propose that formamidines interact with octopamine-sensitive adenylate cyclase, the enzyme that catalses the production of cyclic AMP and functions as an intracellular messenger.
6.8.2 Avermectins
1. General Properties: This is a new family of insecticidal, acaricidal, and antihelminthic agents that have been isolated from fermentation products of the soil bacterium Streptomyces avermitilis. Avermectins are extremely complex and production relies on the processing of fermentation products from the bacterium. Several different avermectins have been isolated although one of the most active components is avermectin Bl. The avermectins are extremely effective insecticides although marketing of these compounds has been limited and their use has been primarily as an antihelminthic in the livestock industry.
3. Mode of Action: Most work to date supports the view that Gamma amino butyric acid avermectins block signal transmission from interneurons to excitatory neurons that have GABA as neurotransmitter. However, the exact nature of this interaction remains uncertain. Unlike the cyclodienes which also interact at the GABA receptor ionophore, the avermectins 4. are generally thought of as GABA agonists. They may interact directly with the GABA receptor thereby increasing chloride conductance or they may act at an allosteric binding site and increase the inhibitory effect of GABA. Other reports indicate that avermectins and cyclodienes act similarly.
6.8.3 Spinosad
1. General Properties: This compound is derived from fermentation products of the bacterium, Saccharopolyspora spinosa. The active ingredient consists of two compounds referred to as sponosyn A and D. Spinosad acts as both a contact and stomach poison, although it is generally more active when ingested. It has shown activity against many insect orders including Coleoptera, Diptera, Hymenoptera, Isoptera, Lepidoptera, Siphonoptera and Thysanoptera. Although the material degrades rapidly in the environment, residual activity is comparable in the laboratory to other commonly used synthetic insecticides. Current registrations of this product include. 2. Mode of Action: Spinosad mode of action has has been the subject of recent debate, but recent evidence suggests that its primary site of activity involves the acetylcholine receptor. a) Symptomology: Spinosad affects the insect nervous system and is fact acting. The symptomology of insecgs treated with spinosad is distinctly different than for conventional insecticides. Spinosad causes excitation of the insect nervous system, leading to involuntary muscle contractions, prostration with tremors and finally paralysis. 22
b) These effects are consistent with the activation of nictinic acetylcholine receptors (acetylcholine agonsist) by a mechanism that is novel and unique among known insect control products. Spinosad affects the nicotinic acetylcholine receptors by a mechanisms that is different from other nicotinic receptor-based insecticides (imidacloprid and nictoine). Spinosad also has effects of GABA receptor function that may contribute further to its insect activity. The exact site on the GABA receptor-ionophore that interacts with Spinosad is uncertain although preliminary information indicates that is is different from both cyclodienes and avermectins based on cross resistance spectra.
6.8.5 Chloronicotinyls
During the 1970s, a new chemical class of insecticides, the heterocyclic nitromethylenes, were discovered by a group of chemists at Shell. Preliminary investigations with this chemistry revealed good insecticidal but rather poor photostable properties. In 1985, chemists working the heterocyclic nitromethylene chemistry in Japan, synthesized the first member of the new chloronicotinyl group of active ingredients (closely related to the heterocyclic nitromethylenes), imidacloprid. (Admire)
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Strictly speaking, the mode of action of the chloronicotinyls is not new. Nicotine, which has the same mode of action, has been used a natural insecticide for centuries. Nictotine acts not only on the same moleuclar receptors, but probably also binds to the same site as imidacloprid. The mode of action of these compounds is as acetylcholine agonists since their binding to acetylcholine receptors mimics the effects of acetylcholine.
6.5
million people suffered from pesticide poisoning, and 40 000 of the cases were fatal (Schoubroeck et at. 1990). Because of their toxicity, many types of pesticides, e.g DDT, have been banned in industrialized countries. However, organochlorines are still being used in many developing countries. Over time, pests build up resistance to pesticides, which must then be used in ever higher doses to have effect. Eventually, new pesticides must be developed- a very expensive process. Pest resistance builds up more rapidly in tropical than in temperate climates, as biological processes are more rapid at higher temperatures. In 1984, resistance to pesticides was known for 447 insects and mites, 100 plant pathogens, 55 kinds of weeds, 2 kinds of nematodes and 5 kinds of rodents (Gips 1987). Many pesticides cause the development of resistance in populations of organisms; many species of insects, mites, nematodes, micro-organisms and weeds have acquired a degree of resistance against one or several types or chemical groups of pesticides. These chemicals become, gradually, less effective, which necessitates the application of higher dosages, higher application frequencies and mixtures, and rapid replacement of those chemicals with new products. This is the so-called pesticide treadmill Pesticides kill not only organisms that cause damage to crops but also useful organisms, such as natural enemies of pests. Chemical insecticides generally more adversely affect natural enemies than the target pest. Because predators and parasitoids must search for their prey, they generally are very mobile and spend a considerable amount of time moving across plant tissue. This increases the likelihood that they will contact the insecticide. When an insecticide is applied, ideally only the target pest(s) should be affected. The goal is to maximize pest mortality while minimizing harm to natural enemies. The incidence of pest attacks and secondary pest attacks may increase after pesticides have killed the natural enemies. Only a small proportion of the pesticides applied in fields reaches the organisms that are supposed to be controlled. The major part reaches the air, soil or water, where it has a damaging effect on living organisms. Aquatic organisms are particularly sensitive to pesticides. Pesticides that do not break down easily are absorbed in the food chain and cause considerable damage to insects, insect-consuming animals, prey birds and ultimately, human beings.
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Pesticides, in particular broad-spectrum insecticides and miticides having a persistent activity, may destroy the natural enemy complex. Secondary pests, thus freed from their controlling factors, may then become major pests, or species that hitherto had no economic importance may suddenly assume such importance (e.g. cotton whitefly).
Improper application of pesticides may cause unwanted or hazardous effects. With regard to the specific sensitivity of the target organisms and natural enemies, pesticidal selectivity and dosages need to be taken into account, whereas application technology must correspond with their behaviour and environmental conditions. Thus, a profound knowledge and skill is needed for the responsible use of chemical control, qualities which are often scarcely available among farmers and plant-protection technicians in developing countries.
The cost of pesticides is rising steadily; the average wholesale prices for well-established insecticides rose about 20% in the period 1970-1977. This trend has continued since then and is adversely affecting farmers as farm crop prices generally remained static and levels below the world market values. The increasing complexity of newer insecticides requiring a higher investment in research and manufacturing results in higher retail prices for the user.
The inherent toxicity of pesticides and their often long persistence is a cause of many accidents involving mankind and non-target animals, and a grave source of environmental contamination.
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(2)
Technical grade carbofuran is a crystalline solid having an acute oral toxicity of 3mg/kg (Rats) and a dermal toxicity of 2250 mg/kg (Rabbits) For carbofuran 3%G, the oral toxicity of the formulation would be LD50 (Oral) = 8 X 100 = 800 3 3 Dermal toxicity (Rabbit) = 266.6 mg/kg
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chemistry of the active ingredient toxicology of the active ingredient efficacy of the product on the pest the effect of the product on the plant, animal or surface the effect of the product on the environment the application technique (equipment) the application rate
A formulation consists of one or more active ingredients (a.i.) plus inert ingredients (materials with no pesticidal action). An inert ingredient may be talc in a dust formulation or petroleum distillate in an emulsifiable concentrate formulation. It may be necessary to include other inerts such as solvents, wetting agents, extenders or emulsifiers. A formulation is developed to make the product safer and more convenient to use. Some products are ready to use and require no further mixing although most products applied in the liquid form require dilution in water or oil before use. Formulations can be subdivided into solids, liquids and gases. Dusts or Powders, Granules, Pellets, Tablets, Particulates, Dry Flowables Suspensions (Flowables), Solutions, Emulsifiable Concentrates Fumigants sold as liquids or solids
6.4.1 ABBREVIATIONS
Abbreviations are often used behind the trade name on the pesticide label to indicate type of formulation:
D DF EC F G P S
Sc Sn SP WDG WP WS
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Sprayable Concentrate Active Solution Soluble Powders Water Dispersible Granules Wettable Powders Water Soluble Concentrate
The following chart summarizes formulation types and lists some of the advantages and disadvantages of each type.
Emulsifiable Concentrate
Microencapsulate A suspension d Suspension with a.i. in microcapsules giving a slow release of a.i. Suspension or Flowable A cloudy liquid composed of solid particles of a.i. (finely ground) in a liquid. Needs dilution. a.i. is in solution, usually water and when mixed with water remains clear.
Insecticides
Agricultural sprays
See comments on E.C.'s. Requires little agitation when added to water in spray tank.
Possibly corrosive
Agricultural sprays
Ultra-low Volume Solution af a.i. Use without (ULV) Concentrate designed to be mixing. used undiluted only in ULV equipment. Very high concentrate of a.i.
Concentration of active ingredient during application makes them hazardous. Special equipment required.
GASES
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NAME
DESCRIPTION
ADVANTAGES
TYPICAL USE Greenhouses Mushroom houses Other structures Bulk containers (ships, rail cars, etc.)
Fumigant Volatile liquids or Toxic to many s solids packaged for forms of the pest at release as a gas one time. Penetrates cracks and crevices.
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SOLIDS
NAME DESCRIPTION ADVANTAGES Less dusty than WP formulations and easier to handle DISADVANTAGES TYPICAL USE Dry Flowable A wettable powder which is formulated into small pellets or granules Dust or Powder Requires agitation in Agricultural spray tank pesticides
A finely ground dry Ready to use material of a low concentration (a.i.) plus inerts such a talc. No dilution needed before use. A mix of dry, large, free-flowing particles usually with a low concentration of a.i. Now mixing required. Ready to use. Drift minimal. One step application. Low a.i. concentration. Not dusty
Dusty. Drifts and very Spot visible on surface. treatment Animal powder
Granular
Some dust. Requires Soil special application treatment for equipment. insect or vegetation control Could clog equipment Agricultural soil application
Impregnated Granular fertilizer Fertilizer containing low amount of herbicides Particulate or Bait Mixture of large particles not recognized as a pellet or granular formulation. Mixed with edible inerts. Preformed mixture of a.i. and inerts to form spheres or cylinders
Pellet
As above
As above
A finely ground dry Colours seed to material containing distinguish it a dye, usually red from untreated A dry material similar to dust or granules above except it is soluble in water A preformed "tablet" composed of inerts and a.i. a.i. added to powder (clay,talc) contains a wetting and dispersing agent. Forms a suspension in water.
Fumigant
Containers empty Dusty. Requires Agricultural easily. No liquid agitation to remain in sprays spills suspension
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6.4.4 ADJUVANTS
The effectiveness of some pesticides may be improved by the addition of adjuvants to the product in the spray tank. An adjuvant is a substance added to a pesticide spray tank to improve the effectiveness of the active ingredient. An example of a commonly used adjuvant is a surfactant. Surfactants are "surface active agents" whose purpose is to improve pesticide uptake. Adjuvants may improve the effectiveness of a pesticide in the following ways:
Wetting the surface: the spray may stick to the surface better Increasing/decreasing evaporation: an adjuvant may prevent the spray from drying too fast or help it dry more quickly Increasing absorption into the plant: this is important if the pesticide must enter the plant to be effective Improving spray droplet uniformity: this gives more complete coverage of the target surface, placing the pesticide where it can be more effective
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6.4.6 SYNERGISM
At times combining two or more pesticides will provide better control than when each is used alone. This could be a result of synergism. Synergism, or potentiation, is the increased effectiveness achieved when two chemicals are used together compared to their effectiveness when used alone. For example: Chemical A controls 60% of the pest Chemical B controls 20% of the pest Chemical A + B controls 98% of the pest Synergism increases control so that less chemical may be required. Pesticide tank mixes may have synergism if each pesticide controls a different life stage of the pest population. This is an asset
during a busy spray season. It is convenient and economical to combine pesticides so that only one application must be made. Sometimes several types of pests can be controlled at the same time -- insects, diseases and mites.
CONCLUSION Pesticides are integral part of agricultural production. Apart from their importance in helping to increase the world food supply, they safeguard the crop yields, which are necessary to guarantee a minimum profitability to farmers. If agricultural productivity is to be increased to meet rising food demand, and public health improved in tropical areas where insect-borne diseases remain serious problems, the stability of pest control must be a global concern. Since most productive land is already cultivated, and many wilderness areas are threatened by the expansion of agriculture, land already under cultivation must be made as productive as possible. Improving pest control, both pre-and postharvest, is one important means of raising net yields. For example, up to one third of Asian rice production may be lost to insects annually. Even with dramatic increases in pesticide use in recent decades, however, the percentage of crop lost to pests has apparently not declined. Clearly, just pouring on more chemicals is no answer. Pesticides present a dilemma: as their hazards become more apparent, so does the need to use them. Although designed to kill, they are often life-savers. Although increasingly costly, they bring economic benefits. And while they have opened up many possibilities for improving agriculture and public health, they 33
have closed others, making us extremely dependent on them for our continued survival. Can we resolve this dilemma? Can we reduce the risks of pesticide use while retaining the benefits? Must we rely solely on chemicals for effective, affordable pest control? The technologies that can be brought to bear on pest and pesticide management, shows that we can better manage pests without excessively polluting the earth and us. Pest-control methods themselves are not inherently safe or risky: the way the method is applied determines risk. To summarize, pesticides are efficient tools for preventing crop losses due to plant pest and diseases. They enable farmers to produce regularly, good yields of high quality crops. Furthermore, they contribute to the rationalization and intensification of farming and to more effective harvesting. In Summary
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