MXPA00007665A - Enhancement of metal molluscicides by ethylene diamine disuccinic acid - Google Patents

Abstract

An ingestible mollusc poison contains a simple metal compound, an activity enhancing additive suchas ethylene diamine disuccinic acid (EDDS) and derivatives thereof, and a carrier material edible to molluscs. In one embodiment the active agent of the mollusc poison may be in the form of a metal complex of EDDS. The composition may be used alone or in conjunction with molluscicidal co-active agents and/or fertilizers.

Description

IMPROVEMENT OF METALLIC MOLUSCICIDES BY ACID ETILEN DIAMIN DISUCCINC FIELD OF THE INVENTION This invention relates to compounds for pest control and more particularly to effective compositions for controlling mollusc pests by improving the effectiveness of metal poison absorption in molluscs. BACKGROUND OF THE INVENTION Terrestrial pulmonate gastropods such as slugs and snails are significant plant pests that affect commercial agriculture and horticulture and home gardens. These organisms are omnivorous and consume large amounts of vegetative matter during their daily forage. Consequently, they can seriously damage plant gardens and even plant crops during all phases of the growth cycle. Due to the destructive potential, control measures should be employed to ensure adequate protection of growing plants. Aquatic molluscs include the fresh water snails Bulilsu sp., Bulinus, Biomphalaria, and Oncomeania, and vectors of parasitic worms (for example, Schistosoma), are also pests. Aquatic mollusks are controlled by a number of synthetic and botanical compounds. The terrestrial pulmonate gastropods and aquatic molluscs are collectively referred to herein as mollusks. A wide variety of approaches have been used to combat mollusc pests. Probably the most common is the use of poisonous compounds called molluscicides. Molluscicides encompass a diverse group of chemical compounds including calcium table salt (NaCl) arsenate, copper sulfate and metaldehyde. Molluscicides, depending on their mode of action, fall into two main groups: (1) contact poisons or (2) ingested poisons. As a contact poison, the molluscicides must come into physical contact with the outside of the mollusk, either by external application or as a result of the mollusc running the bait on the ground. The venom is picked up by the mollusc's proteinaceous mud coating and accumulates in the body of the mollusk until it reaches lethal proportions. One of the main disadvantages of contact type molluscicides is that they have very little effect if mollusks are not physically touched by the chemical. Slugs or snails will not be affected if they are hidden or migrate in an area after application of contact molluscicide.

One of the few compounds that act as much as a contact poison as ingested is metaldehyde. This compound is commonly used in long-term bait, attracting molluscs and exterminating them after ingestion of the compound. Despite its high effectiveness and commercial popularity, metaldehyde is toxic to higher mammals and is a major contributor to the poisoning of domestic animals in the U.S.A. and Europe. Heavy metals, including zinc, aluminum, copper and iron, are all toxic to molluscs and are known as effective molluscicides when used as contact poisons in the form of salts or chelates (Henderson, et al., 1990). Few of them, however, have been commercially successful, probably because many of these compounds are not palatable to mollusks and are not ingested in sufficient quantities to be effective. More recently Henderson et al. (In UK Patent Application UK 2 207 866A, 1988) discovered that specific aluminum complexes with pentadione and iron compounds with nitroso compounds will act as both ingested and contact poisons. The U.S. Patent No. 5,437,870 (Puntch et al.) Discloses an ingestible molluscum venom having a carrier (e.g., a bait), a simple iron compound, and a second component. The second component can be ethylene diamine tetraacetic acid (EDTA), salts of EDTA, hydroxymethylene triamine diacetic acid (HEDTA) or salts of HEDTA. The patent application Australian No. 77420/98 also describes an action molluscicide in the stomach, which includes a metal complexone (ie iron EDTA) and a carrier. With ingested poisons based on metal, the slug must eat and absorb the poison in quantity large enough to reach a lethal threshold. These compounds are much more difficult to formulate and use than contact poisons, because the compounds are not always pleasant to the palate of slugs. To be effective, these compounds must be ingested and digested within the digestive tract of the mollusk at levels sufficiently high to cause a pesticidal effect. However, the activity of these molluscicides must be slow enough in action to prevent the slug from getting sick prematurely and stop feed on the poison before a lethal dose is ingested, (Henderson and Parker, 1986). Many of the contact poisons (eg aluminum sulfate, copper sulfate, borax, etc.) are useless as ingested poisons due to their dissipation to slugs.

DE 195 18 150 Al describes a microbiological process for preparing (S, S) -EDDSA having good properties for complex formation, and is biodegradable. This compound is suggested as a more convenient complexing agent in domestic washing compositions than EDTA and NTA, since these latter two are only slowly biodegraded. JP 53 038624 A describes a pesticidal composition usable against slugs containing triallyl isocyanurate. WO 89 01287 A describes the use as molluscicide of an aluminum (III) chelate with a ligand of the formula [R ^ OCHCOCR2] "(R1 and R2 = methyl, ethyl, propyl, methoxyethyl, ethoxyethyl, dimethoxymethyl or diethoxymethyl) or iron (III) with a ligand of the formula [R3NO.N = 0] ~ (R3 = alkyl with 1 to 6 carbon atoms branched when containing more than 4C) KHIM.SEL.KHOZ., vol.23, no. 8, 1985, pages 15-22 is related to the use of microelement fertilizers containing Fe, Co, Zn, Mn, Mo, Mg, Cu and B to increase the total content of sugar, protein, starch, fat and sugar content. vitamins and produce various crops.Micro elements were frequently used with, among others, EDDSA, ethylen diamin disuccinic acid.

There is no mention of an edible mollusc carrier material, used. In this way, it would be convenient to provide a composition that improves the absorption of mollusc poisons of stomach action without deterring the ingestion of the venom by molluscs. SUMMARY OF THE INVENTION The invention provides a venom composition for the stomach of molluscs, comprising a simple metal compound, an adhesive that improves the activity and absorption of the metal and a carrier material that is edible to molluscs. The composition is effective to exterminate mollusks, when ingested by the mollusk. The simple metal compound. it can include metals selected from the group consisting of iron, copper, zinc, aluminum and their mixtures. The term "iron" as used herein is understood to refer to both iron and ferrous forms of iron. The activity enhancing additive is a compound selected from the group consisting of ethylene diamin disuccinic acid, isomers of ethylene diamin disuccinic acid, salts of ethylene diamin disuccinic acid, metal complexes of ethylene diamin disuccinic acid and mixtures thereof. The carrier material is one that is edible for molluscs and preferably is a shellfish feed.

In another embodiment, the composition comprises a metal complex of ethylene diamin disuccinic acid or its isomers. Metals from which the complex can be formed include iron, copper, zinc and aluminum. In another embodiment, the mollusc venom composition may also include a co-active ingredient such as metaldehyde. In yet another embodiment, the composition may include or be employed with a fertilizer compound such as a granular fertilizer. As used here, the term? molluscum? it refers to both terrestrial and aquatic molluscs. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a composition that is an ingestible poison for molluscs. In one embodiment, the composition includes a simple metal compound, an additive that improves the activity that is considered to increase the effectiveness of the metal compound, and a carrier that is edible to the molluscs. Additional additives that improve the formulation can be included equally. Examples of these compounds include compounds for pH adjustment, preservatives, antimicrobial agents, phagostimulants, and flavor-altering additives. The simple metal compound can be one that includes metals such as iron, copper, zinc, aluminum or their mixtures. This compound can be reduced elemental iron, metal proteins (for example iron proteins, copper proteins, zinc proteins and, aluminum proteins, (metal salts) for example iron salts, copper salts, zinc salts, aluminum salts and their mixtures (metal carbohydrates) for example iron carbohydrates, copper carbohydrates, zinc carbohydrates, aluminum carbohydrates and mixtures thereof). Specific examples of these compounds include iron acetate, iron chloride, iron phosphate, mixtures of iron phosphate / sodium citrate, sodium iron phosphate, iron pyrophosphate, iron nitrate, iron ammonium sulfate, iron albuminate , iron sulfate, iron sulfide, iron choline citrate, iron glycerol phosphate, iron citrate, iron ammonium citrate, iron fumarate, iron gluconate, iron lactate, iron saccharate, iron fructate, dextrose iron, iron succinate, iron tartrate, copper acetate, copper chloride, copper phosphate, copper pyrophosphate, copper nitrate, copper ammonium sulfate, copper albuminate, copper sulfate, copper gluconate, copper lactate , copper saccharate, copper fructate, copper dextrat, zinc acetate, zinc chloride, zinc phosphate, zinc pyrophosphate, zinc nitrate, zinc ammonium sulfate, zinc albuminate, zinc sulfate, zinc gluconate, lactate zinc, zinc saccharate, zinc fructate, zinc dextrate, aluminum acetate, aluminum chloride, aluminum phosphate, aluminum pyrophosphate, aluminum nitrate, aluminum ammonium sulfate, aluminum albuminate, aluminum sulfate, gluconate Aluminum, aluminum lactate, aluminum saccharate, aluminum fructate and aluminum dextrose. It is understood that the term "iron" as used herein, refers to both ferric and ferrous forms of this element. As noted above, the additive that improves the activity is that which improves the efficiency of the metal compound by improving the digestive absorption of the metal. An additive that improves the preferred activity is ethylene diamine disuccinic acid (EDDS), both in its naturally occurring and synthetic forms. In addition, the additive that enhances the activity may be in the form of isomers of ethylene diamin disuccinic acid, salts of ethylene diamin disuccinic acid, metal complexes of ethylene diamin disuccinic acid and mixtures thereof. Additives that enhance activity such as EDDS, its isomers, and its derivatives, are considered to contribute to the rapid absorption of the simple metal compound in the digestive tract of the mollusk, in the internal organs of the animal. This results in irreversible rapid destruction of the cellular integrity of the mollusk that avoids its continuous feeding into plant material, eventually leading to death. EDDS is considered to affect parts of the digestive system of the mollusk, by allowing the metal to be dispersed more freely and rapidly through the body of the mollusk body. The result of this overload of metal results in pathological danger to the mollusk system. EDDS is a hexadentate ligand that occurs naturally and that is produced by a number of microorganisms, including the actinomycete, Amycolatopsis japonicum sp. nov. (Nishikori et al J. Antibiot 37: 426-427 (1994); Goodfellow et al., Systematics and Applied Microbiology (Systematic and Applied Microbiology) 20: 78-84 (1997). The molecular formula for this compound is C10H16N2O2 for the acid and C10H13N2O8Na3 for the trisodium salt. The acid has a molecular mass of 292.25 while the trisodium salt is 358.19. The compound can occur in three stereoisomers, [R, R], [R, SIS, R], and [S, S]. EDDS can also be synthesized by reaction of L-aspartic acid and 1,2-dihaloethane, as described in US Pat. No. 5,554,791. EDDS has been commercially developed as a trisodium salt compound sold under the trademark Octaquest ™ E-30 by Associated Octel Company Ltd. This compound has a capacity to cope with metals to serve as a chelator. It has the advantage of easily biodegrading and does not persist from the environment (Schowanek et al., Chemosphere 34: 2375-2391 (1997)). Therefore, it has been compounded to be used as a surfactant in laundry detergents as described in U.S. Pat. No. 4, 7 ??, 233. Useful salts of ethylen diamin disuccinic acid which can serve as an additive that improves activity according to the present invention include alkali metal salts, alkaline earth metal salts, ammonium salts and salts of substituted ammonium of this compound, as well as their mixtures. Preferred salts include the sodium, potassium and ammonium salts. The additive which improves the activity may also be in the form of metal complexes of ethylene diamin disuccinic acid. Examples of these complexes include EDDS iron complexes, as well as EDDS copper, zinc and aluminum complexes. In one embodiment, the composition can be employed without a simple metal compound as a separate component. On the contrary, the compound can be used in the form of an EDDS metal complex, with metals selected from iron, copper, zinc and aluminum. Suitable carrier materials are those that are edible for molluscs. Mollusk foods are examples of a preferred type of carrier material. Examples of suitable mollusc food carriers include wheat flour, wheat cereal, agar, gelatin, oil cake, pet food wheat, soy, oats, corn, citrus paste, rice, fruits, fish by-products, sugars, coated vegetable seeds, coated cereal seeds, casein, blood meal, bone meal, yeast, fats, beer products and their mixtures. Examples of particularly useful mollusc foods include a mixture of wheat flour-bone meal, which has a ratio of bone meal to wheat flour in the range of 50:50 to 90:10 and one formed from wheat flour. wheat and sugar in a ratio of wheat flour to sugar in the range of approximately 90:10 to 95: 5. Other compounds, as noted above, can be added to the composition as additives that improve the formulation. These compounds include preservatives or antimicrobial agents, phage stimulants, water impermeable agents, additives that alter taste or taste, and additives for pH adjustment. Exemplary conservatives include MKMR, available from Rohm & Hass Company of Philadelphia, Pennsylvania, and CA-24, available from Dr. Lehmarm and Co. of Mernmingen / Allgáu, Germany. Preservatives such as these can normally be mixed with water to form a solution of material that is added to the solution at a concentration in the range of about 10-750 ppm. Fago-stimulants can be added to the composition to attract molluscs and induce molluscs 5 to feed on the composition. A variety of phagostimulants can be employed including sugars, yeast products and casein. Sugars such as sucrose are among the most preferred phagostimulants. These additives are usually incorporated into the composition in a dry form. Typically, about 1 to 2.5% by weight of the total composition can be added to the composition. Water-impermeable agents can also act as binders, can be added to the composition to improve the weatherability of the composition. These typically are water insoluble compounds such as waxy materials and other hydrocarbons. Examples of waterproofing agents Suitable JPs are paraffin wax, stearate salts, wax of bees and similar compounds. A preferred wax compound is PAR0WAX11MR, available from Conros Corp. of Scarborough, Ontario, Canada. Water-impermeable agents can be incorporated in the composition in dry form, at 5 to 12% by weight of the total composition.

It is also convenient to include flavor-altering compounds within the composition, which make the composition unpalatable to the palate for animals such as humans and pets. Exemplary compositions include those that have a bitter taste. Such a compound is commercially available as BITREXMR from McFarlane Smith Ltd. of Edinburgh, Scotland. These compounds are typically added at a very low concentration. For example, a 0.1% BITREX solution may be added to the composition approximately 1 to 2% by weight of the total composition. Useful pH-affecting additives include calcium carbonate, potassium carbonate, potassium hydroxide, ascorbic acid, tartaric acid and citric acid. These additives can be used in a concentration in the range of about 0.2 to 5.0% by weight and should be effective to adjust the pH in a range of about 5 to 9. The molar ratio of the metal in the simple metal compound to the additive that improves the activity, it can be in the range of approximately 1: 0.02 to 1:58. More preferably, this ratio is in the range of 1: 0.3 to 1:12. In addition, the metal in the simple metal compound may be present in a concentration range of about 200 to 20,000 ppm (0.02 to 2.0% by weight), while the additive that improves the activity may be present in a concentration in the range from about 2,000 to 60,000 ppm (0.2 to 6.0% by weight of the composition). An exemplary concentration range is about 0.1 to 0.5% by weight of the composition for the metal and about 0.8 to 6.0% by weight for the EDDS component. When the composition is employed without a simple metal compound, ie in the form of an EDDS metal complex, the metal complex may be present from 5000 to 90,000 ppm (0.5 to 9.0% by weight). In one embodiment, the composition may also include a co-active molluscicidal agent. A co-active molluscicidal agent such is metaldehyde. Other potential co-active molluscicidal agents include methiocarb, carbaryl, isolan, mexcarbat, niclosamide, trifenmorph, carbofuran, anacardic acid and saponins derived from plants. These co-active ingredients can be added to the composition at a concentration in the range of about 0.2 to 5.0% by weight. In yet another embodiment, the composition may also include a fertilizer such as, eventually, any plant fertilizer. Convenient fertilizers are typically granular and one example of a useful fertilizer is Ironitell ™, available from Ironite Products Company of Scottsdale, Arizona. When present, the fertilizers can be used at a concentration in the range of about 0.5 to 10.0% by weight of the composition. The composition of the invention is typically used in dry form and many of the constituent ingredients of the composition are included in dry form. However, it is often useful to include a sufficient amount of water within the composition, to form a dough so that the ingredients can be mixed more easily. Typically water is added at a concentration of about 15 to 60% by weight of the total composition. However, water is typically displaced by heating and drying molluscicide bait before it is used. The composition can also formulated as a liquid, especially when the composition uses an EDDS metal complex. As noted above, the composition of the present invention is typically employed in a dry form,? dispersible such as powders, granules, cubes or nodes.

The composition can be dispersed in or around areas infested with molluscs as well as in areas where shellfish infestation is to be avoided. When used to combat aquatic molluscs, the composition can simply be added to the environment inhabited by mollusks.

To prepare the composition, a convenient amount of the simple metal compound and the additive that improves the activity can be mixed in dry form with a dry carrier material. Subsequently, other dry ingredients (such as phago-stimulants and water-impermeable agents) are mixed and added with bait. Next, convenient amounts of liquid additives (such as preservatives, taste-altering additives and water) are added to the dry mix to form a dough. Bait can be covered, such as with a plastic wrap and heated. A preferred heating technique is when heating in a microwave oven with 30 seconds to 10 minutes. After heating, the web can be processed in a food mill to obtain strands of the molluscicide composition. This material is then dried, at elevated temperatures or environments and can be formed into a desired shape such as powders, nodules or granules. An exemplary molluscicide composition can be prepared as follows. First, metal compounds, for example iron salts or iron carbohydrates, are mixed dry in a cereal flour (wheat) between 1,000 to 20,000 ppm w / w of metal. EDDS, or its sodium salt is then added to the flour in a molar ratio to the amount of iron added. This level can vary in the range of a metal molar ratio: EDDS in the ratio of approximately 1: 0.02 to 1:58. The EDDS is added to the mixture while it is continuously stirred. Other ingredients can be added to the mixture such as antimicrobials ((Legend), water-impermeable agents and phago-stimulants (eg sugar). Water-soluble additives are dissolved in water and then the water is mixed in the dry iron / wheat compounds more EDDS mix The dough is mixed thoroughly in a milling device and extruded into the noodle form The resulting bait is dried at 40 celsius for 24 hours before testing Metal complexes can be synthesized by combining virtually any soluble metal compound , such as ferrous sulfate with soluble EDDS or virtually any soluble EDDS derivative Following this combination, the pH can be adjusted (for example in the range of about 5 to 9) with a convenient agent such as a concentrated potassium hydrogen solution. Exemplary metal compounds include reduced elemental iron, metal proteins (eg, iron proteins, copper proteins, protein s of zinc, aluminum proteins) metal salts (eg, iron salts, copper salts, zinc salts, aluminum salts and mixtures thereof) metal carbohydrates (eg iron carbohydrates, copper carbohydrates, zinc carbohydrates , aluminum carbohydrates and their mixtures). Specific examples of these compounds include iron acetate, iron chloride, iron phosphate, iron phosphate / sodium citrate mixture, iron and sodium phosphate, iron pyrophosphate, iron nitrate, iron ammonium sulfate, iron sulfide , iron albuminate, iron hill citrate, glycerol iron phosphate, iron citrate, iron ammonium citrate, iron fumarate, iron gluconate, iron lactate, iron saccharate, iron fructate, iron dextrus, iron succinate, iron tartrate, copper acetate, copper chloride, copper phosphate, copper pyrophosphate, nitrate copper, copper ammonium sulfate, copper albuminate, copper sulfate, copper gluconate, copper lactate, copper saccharate, copper fructate, copper dextrate, zinc acetate, zinc chloride, zinc phosphate, pyrophosphate zinc, zinc nitrate, zinc ammonium sulfate, zinc albuminate, zinc sulfate, zinc gluconate, zinc lactate, zinc saccharate, zinc fructate, zinc dextrate, aluminum acetate, aluminum chloride, aluminum phosphate , aluminum pyrophosphate, aluminum nitrate, aluminum ammonium sulfate, aluminum albuminate, aluminum sulfate, aluminum gluconate, aluminum lactate, aluminum saccharate, aluminum fructate and aluminum dextrate. Exemplary EDDS derivatives include ethylene diamin disuccinic acid isomers, ethylene diamin disuccinic acid salts, including alkaline earth metal, alkali metal, ammonium, substituted ammonium, mixtures of these salts, metal complexes of ethylene diamines disuccinic acid and mixtures thereof. The following non-limiting examples serve to further illustrate the present invention. Example 1 A tub test is configured or arranged with 20 Deroceras reticulatum and two lettuce plants per tub with three tubs for iron treatment and two tubs for controls. Composta is used to cover the bottom of the tubs. Slugs were collected from the field and added to the tubs along with two grams of bait. Baits of the type noted in the table below were made the day before use.

* Unless noted otherwise, controls made with flour and sugar, contain 94 parts of flour 6 parts of sugar.

The vats were kept in the greenhouse during the evaluation period. The data were collected at 3 and 7 days after treatment and the results obtained are illustrated below in Tables 1 and 2. Table 1. Observations on mortality at 3 DAT * * DAT = D as after treatment Table 2. Observations on mortality at 7 DAT.

Example 2 A tub test is performed with 15 Deroceras reticulatum and two lettuce plants per tub with two tubes per treatment. Compost is used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubes along with two grams of bait. EDDS of iron was synthesized from EDDS and iron chloride. Baits of the type noted in the Table below were made the day before use.

The vats were kept in the greenhouse during the evaluation period. The data were collected at 3 and 6 days after treatment and the results obtained are illustrated below in Tables 3 and 4. Table 3. Observations on mortality at 4 DAT. ft Table 4. Observations of mortality at 6 DAT A tub test is configured with 15 Deroceras reticulatum, two lettuce plants per tub and two tubs per treatment, except for the aluminum nitrate treatment that had a replica of 22 slugs. Compost is used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs along with 20 grams of bait. The tubs were kept out during the experiment. Bait of the type noted in the table below is made the day before use.

The vats were kept in a greenhouse during the evaluation period. The data was collected on days 3 and 7 after treatment and the results obtained are illustrated below in Tables 5 and 6.

Table 5. Observations of mortality at 3 DAT Table 6. Observations of mortality at 7 DAT Example 4 A tub test is constituted with two replicates per treatment of 10 Arion ater. Two lettuce plants were placed in a tub. Compost is used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs or together with 5 grams of bait. The vats are kept out during the experimental period. Bait is made by dissolving EDDS of sodium, sugar, iron in water, adding flour and then adjusting the pH with K2C03. The tubs are kept out during the experiment. Baits of the type noted in the table below are made the day before use. 8A R4 / 139/1, 0.28% iron (iron sugar) + 1.08% NaEDDS, pH 7.33 8B R4 / 139/2, 0.28% iron (iron sugar) + 1.08% NaEDDS, pH 8.45 8C R4 / 139/3, 0.28 % iron (iron sugar) + 1.08% NaEDDS, pH 9.53 8D R4 / 139/4, 0.28% iron (iron sugar) + 1.08% NaEDDS, pH 10.5 The vats were kept outside during the evaluation period. The data was collected at 4 and 6 days after treatment and the results obtained are illustrated below in Tables 7 and 8. Table 7. Observations of mortality at 4 DAT Table 8 Mortality observations at 6 DAT Example 5 A tub assay was arranged with two replicates per treatment of 10 Arion ater. A large cabbage plant was placed by tube. Compostas was used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs along with 5 grams of bait.

Tubs were kept outside during the experimental period. Bait of the type noted in the table below was prepared the day before use. 7A R4 / 138/4, 2800 ppm iron as iron phosphate + 1.08% EDDS 7B R4 / 140/1, 2800 ppm iron as iron phosphate + 2.5% EDDS 7C R4 / 138/1, 4000 ppm iron as iron phosphate + 2.5% EDDS 7D R4 / 138/2, 4500 ppm iron as iron phosphate + 2.5% EDDS 7E DSA / 120 / l, control bait made with flour and sugar The vats were kept outside during the evaluation period. The data were collected at 4 and 7 days after treatment and the results obtained are illustrated below in Tables 9 and 10. Table 9. Observations of mortality at 4 DAT Table 10: Observations on mortality at 7 DAT Example 6 A standard tub test was set up with 15 Deroceras reticulatum and one lettuce plant per tub and two treatment tubs. Compost was used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs together two grams of bait. The vats were kept outside during the experimental period. Bal the type noted in the table below are made the day before use.

Bait code 6A R4 / 155/1, 0.28% iron as iron phosphate and 1.50% EDDS 6B R4 / 155/2, 0.28% iron as iron phosphate and 1.75% EDDS 6C R4 / 153/1, 0.28% iron as phosphate of iron and 2.25% EDDS 6D R4 / 155/3, 0.28% iron as iron phosphate and 2.75% EDDS 6E R4 / 140/2, 0.28% iron as iron phosphate and 3.00% EDDS 6F DSA / 120/1, bait control made with flour and sugar The data were collected at 4 and 7 days after treatment and the results obtained are illustrated below in Tables 11 and 12. Table 11. Observations on mortality at 4 DAT Table 12. Observations on mortality at 7 DAT Example 7 A standard tub test is set up with 15 Deroceras reticúla tum and one lettuce plant per tub and two tubs per treatment. Composts are used to cover the bottoms of the tubs. Slugs are collected from the field and added to the tubs along with two grams of bait. The tubs were kept outdoors during the experimental period. Slugs of the type noted in the table below are made on the day before use.

The data collected on days 4 and 7 after treatment, and the results obtained are illustrated below in Tables 13 and 14. Table 14. Observations on mortality at 4 DAT ** = 1 missing slug Table 14. Observations on mortality at 7 DAT Example 8 A standard tub test is set up with 15 Deroceras reticulatum and one lettuce plant per tub and two tubs per treatment. Composta is used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs along with 2 grams of bait. The tubs were kept out during the experimental period. Bait of the type noted in the table below is made the day before use.

Data were collected at 4 and 7 days after treatment and the results obtained are illustrated in tables 15 and 16. Table 15. Observations on mortality at 4 DAT Table 16. Observations on mortality at 7 DAT Example 9 A standard tub test is configured with 10 Arion ater and one lettuce plant per tub and per treatment. Compost was used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs along with six grams of bait and two cabbage plants. The vats were kept outdoors during the experimental period. Bait of the type noted in the table below were made one day before use.

The data was collected six days after treatment and the results obtained are illustrated in Table 17 below ¥ 15 Table 17. Observations on mortality at 6 DAT Example 10 A standard tub test is configured with 15 Deroceras reticulatum and one lettuce plant per tub and two tubs per treatment. Composta is used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs along with 2 grams of bait. The tubs were kept outdoors during the experimental period. Bait of the type noted in the table a < Then they were made the day before use.

Bait code 2A R4 / 164/2, 0.28% iron as iron sulphate with 2.25% EDDS at pH 3.58 2B R4 / 167/1, 0.28% iron as iron sulphate with 2.25% EDDS at pH 5.54 2C R4 / 167/2 , 0.28% iron as iron sulfate with 2.25% EDDS at pH 7.34 2D R4 / 167/3, 0.28% iron as iron sulfate with 2.25% EDDS at pH 9.30 10 2E R4 / 167/4, 0.28% iron as sulfate iron with 2.25% EDDS at pH 9.57 2F R4 / 162/2, 0.28% iron as iron phosphate with 2.25% EDDS 2G R4 / 161/6, the control bait. made with flour and sugar The data collected on days 4 and 7 after treatment 15, and the results obtained are illustrated below in Tables 18 and 19. Table 18. Observations on mortality at 4 DAT Table 19. Observations on mortality at 7 DAT Example 11 A test in standard tub is configured with 15 Deroceras reticulatum and one lettuce and one cabbage plant per tub and two tubs per treatment. Composta is used to cover the bottoms of the tubs. Slugs were collected from the field and added to the tubs along with 2 grams of bait. The tubs were kept outside during the experimental period. Bait of the type noted in the table below were made the day before use.

The data were collected at 4 and 7 days after treatment, and the results obtained are illustrated below in Tables 20 and 21. Table 20. Observations on mortality and plant feeding at 4 DAT Having described the preferred embodiments of the invention, it will be apparent to a person of ordinary skill in the art that other embodiments incorporating those concepts may be employed. It is therefore considered that these modalities will not be limited to the described modalities but rather will be limited only by the spirit and scope of the appended claims. All publications and references cited herein are incorporated by reference in their entirety. Unless noted otherwise, all percentages by weight are percent of the total composition.

Claims (25)

1. CLAIMS 1.- A stomach poison composition for molluscs, characterized in that it comprises: a simple metal compound, which includes a metal selected from the group consisting of iron, copper, zinc, aluminum and their mixtures; an additive that improves the activity selected from the group consisting of ethylene diamin disuccinic acid, isomers of ethylene diamin disuccinic acid, salts of ethylene diamin disuccinic acid, metal complexes of ethylene diamin disuccinic acid and mixtures thereof; and an edible carrier material to molluscs, stomach venom for molluscs is effective for determining mollusks upon ingestion by molluscs.
2. 2. The composition according to claim 1, characterized in that the salt of ethylene diamin disuccinic acid is selected from the group consisting essentially of alkali metal salts, alkaline earth metal salts, ammonium salts, substituted ammonium salts and their salts. mixtures
3. 3. The composition according to claim 1, characterized in that it also comprises a co-active ingredient molluscicide.
4. 4. The composition according to claim 3, characterized in that the co-active ingredient molluscicide is selected from the group consisting of metaldehyde, methiocarb, carbaryl, isolan, mecarbate, mercaptodimethur, niclosamide, trifenmorph, carbofuran, anacardic acid, saponins derived of plants and their mixtures.
5. 5. The composition according to claim 1, characterized in that it also comprises an agent for pH adjustment.
6. 6. - The composition according to claim 5, characterized in that the agent for pH adjustment is chosen from the group consisting of calcium carbonate, potassium carbonate, potassium hydroxide, ascorbic acid, tartaric acid and citric acid.
7. 7. - The composition according to claim 5, characterized in that the pH is in the range of about 5 to 9.
8. 8. The composition according to claim 1, characterized in that the molar ratio of metal to the bait additive is in the range of approximately 1: 0.02 to 1:58.
9. 9. - The composition according to claim 1, characterized in that the metal is present in the simple metal compound at a concentration in the range of about 200 to 20,000 ppm.
10. 10. - The composition according to claim 1, characterized in that the additive that improves the activity is present in a concentration in the range of about 0.2 to 6.0% by weight of the copolymerization.
11. 11. The composition according to claim 1, characterized in that the carrier is a mollusk food.
12. 12. - The composition according to claim 11, characterized in that the mollusk food is selected from the group consisting of wheat flour, wheat cereal, agar, gelatin, oil cake, wheat for pet food, soy, oats , corn, citrus paste, rice, fruits, fish by-products, sugars, coated vegetable seeds, coated cereal seeds, casein, blood meal, bone meal, yeast, fats, beer products and their mixtures.
13. 13. - The composition according to claim 11, characterized in that the mollusk food is a mixture of wheat flour-bone meal having a ratio of bone meal to wheat flour in the range of 50:50 to 90 : 10
14. 14. - The composition according to claim 1, characterized in that the simple metal compound is selected from the group consisting of reduced elemental iron, iron proteins, iron salts, iron carbohydrates, copper proteins, copper salts, copper carbohydrates, zinc proteins, zinc salts, zinc carbohydrates, aluminum proteins, aluminum salts, aluminum carbohydrates and their mixtures.
15. 15. - The composition according to claim 1, characterized in that the simple metal compound is selected from the group consisting of iron acetate, iron chloride, iron phosphate, iron phosphate / sodium citrate mixtures, iron and sodium phosphate, iron pyrophosphate, iron nitrate, iron ammonium sulfate, iron albuminate, iron sulphate, iron sulfide, Iron hill citrate, iron glycerol phosphate, iron citrate, iron ammonium citrate, iron fumarate, iron gluconate, iron lactate, iron saccharate, iron fructate, iron dextran, iron succinate, iron tartrate , copper acetate, copper chloride, copper phosphate, copper pyrophosphate, copper nitrate, copper ammonium sulfate, copper albuminate, copper sulfate, copper gluconate, copper lactate, copper saccharate, copper fructate, copper dextrata, zinc acetate, zinc chloride, zinc phosphate, zinc pyrophosphate, zinc nitrate, zinc ammonium sulfate, zinc albuminate, zinc sulfate, zinc gluconate, zinc lactate, zinc saccharate, fructate zinc, zinc dextrose, aceta aluminum, aluminum chloride, aluminum phosphate, aluminum pyrophosphate, aluminum nitrate, aluminum ammonium sulfate, aluminum albuminate, aluminum sulfate, aluminum gluconate, aluminum lactate, aluminum saccharate, aluminum fructate and dextran of aluminum.
16. 16.- A composition, comprising: a fertilizer; and an environmentally compatible molluscicide composition which includes a simple metal compound having metals selected from the group consisting of iron, copper, zinc or aluminum and mixtures thereof, an activity enhancing additive selected from the group consisting of ethylene diamin disuccinic acid, isomers of ethylene diamin disuccinic acid, salts of ethylene diamin disuccinic acid, metal complexes of ethylene diamin disuccinic acid and their mixtures and an edible carrier material for molluscs, the stomach venom of molluscs is effective to exterminate them by ingesting them.
17. 17. The composition according to claim 16, characterized in that the fertilizer is a granular fertilizer.
18. 18. An ingestible molluscicide composition, characterized in that it comprises a compound selected from the group consisting of ethylene diamin ferric disuccinic acid, ferrous ethylene diamines disuccinic acid, ethylene diamin disuccinic acid of copper, ethylene diamin disuccinic acid of zinc, ethylene diamin disuccinic acid of aluminum and its mixtures; and an edible carrier material for molluscs.
19. 19. The composition according to claim 18, characterized in that the carrier material is a mollusk food.
20. 20. The composition according to claim 18, characterized in that it also comprises a co-active molusicidal agent.
21. 21. The composition according to claim 20, characterized in that the co-active moluscicidal agent is selected from the group consisting of metaldehyde, methiocarb, carbaryl, isolan, mexcarbate, mercaptodimethur, niclosamide, trifenmorph, carbofuran, anarcardic acid, saponins derived of plants and their mixtures.
22. 22. The composition according to claim 18, characterized in that the metal is present in the metal compound at a concentration in the range of about 0.5 to 9.0% by weight of the composition.
23. 23. The composition according to claim 18, characterized in that it also comprises a fertilizer material.
24. 24. Method for exterminating unwanted molluscum pests, characterized in that it comprises the steps of: providing a molluscicide composition that includes: a simple metal compound that includes metals selected from the group consisting of iron, copper, zinc or aluminum and their mixtures, an additive activity enhancer selected from the group consisting of ethylene diamin disuccinic acid, ethylene diamin disuccinic acid isomers, ethylene diamin disuccinic acid salts, ethylene diamin disuccinic acid metal complexes and mixtures thereof and an edible carrier material for molluscs; apply the molluscicide composition to an area infested with molluscs and allow the molluscs to ingest the molluscicide composition.
25. 25. A method for killing pests of unwanted molluscs, characterized in that it comprises the steps of providing a molluscicide composition that includes: a metal compound selected from the group consisting of ethylene diamin ferric disuccinic acid, ferrous ethylene diamin disuccinic acid, ethylene diamine acid copper disuccinic, zinc disuccinic ethylene diamin acid, disuccinic ethylene diamin aluminum acid and mixtures thereof; and an edible carrier material for molluscs, applying the molluscicide composition to an area infested with molluscs and allowing the molluscs to ingest the molluscicide composition.