METHODS AND COMPOSITIONS FOR PROTECTING PLANTS AND CROPS

Abstract: Molecular iodine, or a composition or ionic iodine complex which contains, generates, or releases molecular iodine, is used alone or mixed with a carrier for use as a plant and crop protectant. Secondary active ingredients, fertilizers, nutrients, micronutrients, promoters, polyaspartates, biomass, surfactants, emulsifiers, oils, odorants, waxes, salts, preservatives, herbicides, fungicides, nematicides, insecticides, fumigants and iodides are optionally added to the carrier for additional plant benefit. The molecular iodine and the desired beneficial additive(s) is applied directly to plants and/or crops in order to protect the plants and/or crops from pests, such as fungi, nematodes, bacteria and insects, which are harmful to plants and/or crops.

Description: METHODS AND COMPOSITIONS FOR PROTECTING PLANTS AND CROPS Technical Field This invention relates to the use of compositions comprising molecular iodine for protecting plants and/or crops from harmful pests and to methods for use of these compositions. Background of the Invention The protection of plants and crops from pests is of great economic importance to agriculture. In particular, the protection of plants from fungi, nematodes, bacteria and insects is vital to plant life, growth and productivity. An object of the present invention, therefore, is to provide compositions and methods for the use of molecular iodine as a plant and crop protectant. Iodine in commercial products is frequently complexed with added materials. Iodine complexes comprise elemental iodine and a complexing agent for the iodine. Iodine complexes exist in two forms: (1) ionic and (2) nonionic iodine complexes. Ionic iodine complexes typically comprise elemental iodine and a complexing agent for the iodine, i.e., a type I complexing agent, e.g., a cation, or a type II complexing agent, e.g., an organic group comprising an amine. Nonionic iodine complexes, on the other hand, comprise elemental iodine and a type III complexing agent for the iodine. Iodophors and starch-iodine complexes are examples of nonionic iodine complexes. There are numerous examples in the literature describing the preparation and/or uses of nonionic iodine complexes in water purification, wound and skin disinfection, equipment disinfection, germicidal solutions and sanitation; e.g., see U.S. Patent Nos. 2,498,174, 3,244,630, 4,822,592, 4,844,891 and 5,428,050; Japanese patent applications JP 6-172192 A and JP 7-017819 A; and the following technical references: Anon. [Chemical Processing, May (1956), 56-57], A.P. Black et al. [Am. J. Public. Health 49:1060-1068 (1959)], A.P. Black. et al. [J. Am. Water Works Assoc. 57:1401-1421 (1965)], and . Gruening [Specialty Chemicals, August 1996]. For example, CA. Lawrence et al. [J. Am. Phar . Assoc, Sci. Ed. 46:500- 505 (1957)] disclose that nonionic iodine complexes, i.e., type III iodine complexes such as iodophores, e.g., elemental iodine solubilized by complexation with one or more nonionic wetting agents, may be used to protect animals against harmful bacteria, fungi and viruses. However, all of these applications involve the protection of animals, particularly humans, and not non-animals such as plants and crops. There are distinct differences between disinfection applications and plant (or crop) protection applications. First, disinfection targets the control or elimination of pathogens harmful to man or animals. However, many of the compositions useful for disinfection are detrimental to the well-being of plants and/or crops. Therefore, disinfectants and plant (or crop) protectants cannot be used interchangeably. Thus, there is no suggestion that an nonionic iodine complex, when applied to a plant and/or crop, will kill pests detrimental to the plant and/or crop without harming the plant and/or crop. Moreover, the level of nonionic complexed iodine employed for disinfection and purification purposes as practiced in the prior art is relatively constant whereas the levels of iodine employed in the present invention for plant and/or crop protection may vary considerably to take into account many factors, e.g., the type of plant and/or crop to be protected. In contrast, the present invention using molecular iodine, whether complexed or not, provides methods and compositions for plant and/or crop protection against pests harmful only to plants and/or crops while simultaneously not harming the plant and/or crop. Employing organic iodides for controlling plant pathogens has been disclosed; e.g., see U.S. Patent Nos. 3,615,745, 4,977,186 and 5,071,479. For example, U.S. patent No. 5,518,692 to Grech et al. discloses that methyl iodide may be applied to stored crops, such as grains, or directly to the soil as a fumigant (in a manner analogous to the use of methyl bromide) out of the planting season when the soil is idle to control or eliminate plant pathogenic organisms such as nematodes, fungi and weeds. The methyl component of the methyl iodide is the active component with the iodine serving only as a convenient leaving group. For example, removal of the iodide anion from methyl iodide in the presence of sulfur results in methylation of the sulfur. In general, such treatments involve short term exposures to relatively high concentrations of an organic iodide to effect rapid pathogenic organism control or elimination. If the organic iodide is being applied to fumigate the soil, the material is applied while there are no desirable plants and/or crops present to avoid killing them. However, since organic iodides have relatively high volatility and dissipate quickly, they cannot provide long-lasting protection to plants or crops. Moreover, organic iodides, such as methyl iodide, are highly toxic compounds capable of being absorbed into the body by inhalation and by skin contact; therefore, strict precautions to prevent human exposure are mandatory. In contrast, molecular iodine has neither the high volatility nor the high toxicity to humans of organic iodides. Japanese patent application JP 61-183202 A discloses the spraying of an aqueous solution consisting of 1-3% citric acid and 0.2% iodine over the surface of the leaves and stems of field crops for controlling pest damage and diseases. However, the types of crops protected and the amount of solution to be applied to the crops are not disclosed. Moreover, other than a general reference to bacteria, the types of pests and diseases controlled are not disclosed. This reference teaches that the citric acid is the component which is effective against bacteria and pests. This reference further discloses that the effect of the iodine component is to promote the healthy growth of plants. The use of molecular iodine, without a required organic acid co-additive and optionally with a carrier, for plant and/or crop protection against plant and/or crop pests has not been disclosed previously. Summary of the Invention One embodiment of the present invention relates to a method for protecting an agricultural substance selected from the group consisting of plants, crops, harvested crops and mixtures thereof, from pests which are harmful to the agricultural substance. The method comprises selecting a composition which comprises molecular iodine or which, upon application, generates or releases molecular iodine under conditions of normal use and applying the composition to the agricultural substance as many times as necessary per annum in an amount effective to prevent substantial damage to the agricultural substance from the pests. Optionally, at least one additive can be included in the composition which includes the primary active ingredient, molecular iodine, the additive being selected from the group consisting of secondary active ingredients and inert ingredients, with the proviso that the additive is not an organic acid. The secondary active ingredient may be a herbicide, a fungicide, a nematicide, an insecticide or a fumigant. The inert ingredient may be a fertilizer or fertilizer component, a nutrient or micronutrient, a promoter, a polyaspartate, biomass, a surfactant, an emulsifier, an oil, an odorant, a wax, a salt, a preservative or an iodide. The composition may be applied by spraying. The composition may be applied in various ranges depending upon the agricultural substance to which the composition is applied, climate and time of year, among other factors. At least one portion of the plant, which may consist of fruits, vegetables or flowers, may be covered before applying the composition to prevent contact with the composition. In particular, wheat and citrus plants, pecan, peanut, strawberry, blackberry, blueberry, grape, citrus, banana, peach, nectarine, apple, tomato and coffee plants, pine trees, wheat, pecans, peanuts, strawberries, blackberries, blueberries, grapes, citrus fruit, bananas, peaches, nectarines, apples, tomatoes, coffee beans, flowers and softwood products may be protected from pests by application of the composition of the present invention. An additional embodiment of the present invention is directed to a protectant composition for agricultural substances which comprises molecular iodine or which, upon application, generates or releases molecular iodine under conditions of normal use. Optionally, at least one additive can be included in the protectant composition, the additive being selected from the group consisting of secondary active ingredients and inert ingredients, with the proviso that the additive is not an organic acid. The protectant composition may further comprise a carrier present in the form of a liquid or a gas. The liquid carrier may be selected from the group consisting of water, alcohols, oils used in the formulation of agricultural spray emulsions and mixtures thereof. The gaseous carrier may be selected from the group consisting of air, nitrogen, the inert gases and mixtures thereof. Detailed Description of the Invention As used herein, the term "molecular iodine" includes both I 2 and any composition or ionic iodine complex which comprises, generates or releases I 2 . Preferably, the molecular iodine comprises I 2 . Most preferably, the molecular iodine is I 2 . As used herein, the term "iodine complex" is defined as a complex which comprises elemental iodine and a complexing agent for the iodine. Iodine complexes consist of ionic iodine complexes and nonionic iodine complexes. As used herein, the term "ionic iodine complex" is defined as an ionic complex, i.e., comprising elemental iodine and a type I or a type II complexing agent for the iodine which is capable of releasing molecular iodine, i.e., iodine which is titratable with a sodium thiosulfate solution. A standard method for the titration of iodine with sodium thiosulfate is provided in the text "Reagent Chemicals," 8th Edition, American Chemical Society (Publisher), 1993, p. 383. Optionally, the ionic iodine complex can be generated in situ or prior to mixing with a carrier. As used herein, a "type I complexing agent" is represented by M*I". A type I complexing agent forms an ionic iodine complex, which is inorganic and which is represented by M*I" 2n+1 , as follows: M + I" + n I 2 > M + I- 2n+1 (1) where M + is a cation; and n is a number such that n > 1. These ionic iodine complexes are typically prepared by mixing an iodide salt (MI) or hydriodic acid with iodine. Preferably, M is selected from the group which includes Li + , Na + , K + , NH 4 + , H\ 1/2 Ca 2+ , 1/2 Fe + and mixtures thereof. As used herein, a "type II complexing agent", represented by [R-L]*I", is an organic iodide. The positively-charged portion of the type II complexing agent comprises an amine, a sulphide or a sulfoxide, represented by R, and is substituted by a substituent L. A type II complexing agent forms an ionic iodine complex, which is organic and which is represented by [R-L]*I * 2a+1 , as follows: [R-L]*I- + n I 2 > [R-L]*I- 2a+1 (2) where L is hydrogen or a linear, branched or cyclic alkyl cation comprising from about 1 to about 10 carbon atoms formed by removing an iodine anion from an alkyl iodide; and n is a number such that n > 1. These ionic iodine complexes are typically prepared by: (1) mixing R with an alkyl iodide (LI) and iodine, (2) mixing R with hydriodic acid and iodine, or (3) mixing R with an acid, iodide salt (MI) and iodine. Preferably, R is a primary, secondary or tertiary amine, a sulphide or a sulfoxide. Most preferably, R is selected from the group which includes methyl amine, ethanolamine, ethylenediamine, hexamethy lenediamine , aniline, dimethyl amine, diethanolamine , cyclopentyl amine, triethyl amine, tr iethanolamine , pyridine, poly-4-vinylpyridine, piperidine, piperazine, methyl pyrrolidine, polyvinylpyrrolidone, dimethyl sulphide, dimethyl sulf oxide and mixtures thereof . Preferably, L is hydrogen or a linear alkyl cation comprising from about 1 to about 10 carbon atoms formed by removing an iodine anion from an alkyl iodide. Most preferably L is hydrogen. As used herein, the term "nonionic iodine complex" is defined as an organic complex, i.e., comprising elemental iodine and a type III complexing agent for the iodine. Iodophors and starch-iodine complexes are examples of nonionic iodine complexes. As used herein, a "type III complexing agent", represented by R', is an organic material capable of complexing with iodine. A type III complexing agent forms a nonionic iodine complex, which is generally organic and which is represented by R'-I 2 , as follows: R' + I 2 > R'-I 2 (3) Examples of materials useful as R' include starch, methyl amine, ethanolamine, ethylenediamine, hexamethylenediamine, aniline, dimethyl amine, diethanolamine, cyclopentyl amine, triethyl amine, triethanolamine, pyridine, poly-4- vinylpyridine, piperidine, piperazine, methyl pyrrolidine and polyvinylpyrrolidone. These nonionic complexes are typically prepared by mixing R' with iodine. Mechanisms by which compositions or ionic iodine complexes may generate or release molecular iodine include but are not limited to: (1) combining an iodate with a reducing agent, (2) exposing an iodide to a source of photons, e.g., sunlight, (3) combining an iodide and an oxidizer at a pH of 7 or below, (4) further adding a catalyst to (3) , and (5) releasing iodine from an ionic iodine complex. Suitable iodates include but are not limited to potassium iodate, calcium iodate, sodium iodate and iodic acid. Reducing agents include but are not limited to formic acid and a combination of hydrogen and a catalyst. Iodides include but are not limited to inorganic iodides, e.g., KI, Nal and HI; alkyliodides, e.g., ethyliodide; and aromatic iodides, e.g., iodobenzene. Oxidizers include but are not limited to iodates, chlorates, nitrates, peroxides and oxygen. Catalysts include but are not limited to molybdenum, platinum, rhodium, ruthenium and copper. Complexing agents include type I complexing agents, type II complexing agents and mixtures thereof. Preferred type I complexing agents include Li + , Na + , IT, NH 4 + , H + , 1/2 Ca 2+ , 1/2 Fe + and mixtures thereof. Preferred type II complexing agents include methyl amine, ethanolamine, ethylenediamine, hexamethylenediamine, aniline, dimethyl amine, diethanolamine, cyclopentyl amine, triethyl amine, triethanolamine, pyridine, poly-4- vinylpyridine, piperidine, piperazine, methyl pyrrolidine, polyvinylpyrrolidone and mixtures thereof. Although not wishing to be bound by any particular theory, in the present invention molecular iodine is thought to comprise the primary active ingredient of a protectant material which may be applied to or in the vicinity of plants and/or crops and thereby protect plants and/or crops from harmful pests. As used herein, the term "pesticide" is as defined in 40 C.F.R. § 152.3(s) (1996), i.e., any substance or mixture of substances intended for preventing, destroying, repelling or mitigating any pest, or intended for use as a plant regulator, defoliant or desiccant with the exception of those substances specifically exempted in 40 C.F.R. § 152.3 (s) (1 through 3) . As used herein, the term "active ingredient" is as defined in 40 C.F.R. § 152.3(b) (1996), i.e., any substance that will prevent, destroy, repel or mitigate any pest, or that functions as a plant regulator, defoliant or desiccant. As used herein, active ingredients consist of primary active ingredients and secondary active ingredients. Further, the term "primary active ingredient", as used herein, refers to molecular iodine. As also used herein, the term "secondary active ingredient" includes all active ingredients other than molecular iodine. As used herein, the term "pest(s)" for plants and/or crops are the pests as defined in 40 C.F.R. § 152.5 (1996), i.e., vertebrate animals other than man, any invertebrate animal, any plant growing where not wanted and any fungus, bacterium, virus or other microorganism with the exception of those specifically exempted in 40 C.F.R. § 152.5(d). Typical plant and/or crop pests which the compositions of the present invention are effective in protecting against include, but are not limited to fungi, nematodes, bacteria and insects which are harmful to plants and/or crops. Some non-limiting particular applications for these compositions include their use to protect: - harvested bananas from Verticilliu theabromae, Gloeosporium musarum and Fusariu (which cause crown rot) , - banana plants from Mycosphaerella musicola and Mycosphaerella fijiensis (which cause the foliar fungal disease black sigatoka) , - grape plants from Botritis cinerea, Uncinula necator and Rhizopus, - strawberries, blackberries, blueberries and other berries from Botrytis, Altermaria, Rhizoctonia and Mycosphaerella, - citrus plants from Colletotrichum musae and Phytophthora spp. (which cause grey rot) , - pear trees from P. syringae pv. Syringae, - apple trees and peppers from Phytophthora spp. (P. cactorum, P. capsici Leonian) , - vegetables, apple trees and wheat from Pythium (P. ultimum, P. sylvaticum, etc.) and Rhizoctonia (various), - vegetables from Aphanomyces, - corn from European Corn Borer, - corn plants from Corn Root Worm, - celery plants from Septoria apticola, - almond, peach and nectarine trees from Monilia, Sciertinia, Botrytis, Rhizopus and Pseudomonas syringae pv. syringae, - nut trees from Phymatotrichum omnivorum and Xanthomonas campestris pv. Jugandis, - pecan trees from Mycosphaerella, - peanut plants from Cercospora Spp. , - rice plants from Rhizoctonia Spp., Helminthosporiu oryzae, Cercospora oryzae, Rhyncosporium oryzae, Sarocladium oryzae and Entyloma oryzae, - barley plants from Helminthosporium Teres, - wheat plants from Erisiphe graminis, Helminthosporium Teres and Gaeumannomyces graminis var. tritici ("Take All") , - wheat from Russian Wheat Aphid, - flower bulbs and strawberries from Scleronum rolfsii, - flowers and ornamental plants from Botrytis, Altermaria, Rhizoctonia and Scletortinia, - tomatoes, peppers, strawberries and white pine from Fusariu , Fusarium oxysporum f. sp. lycopersici (Fusarium Wilt) , - white pine from Cylindro cladium spp. , - radiata pine tree from Dothistroma septospora, - trees from Gypsy Moth, - rubber trees from Mycrocyclus, - coffee plants from Hemileia Vastratix and Cercospora coffeicola, - cotton from Boll Weevil, Pink Boll Worm and Lygus Bug, - cotton and corn from Boll Worm (also known as Corn Ear Worm) , - cotton, vegetables and ornamentals from Sweet Potato White Fly, and - potatoes and tomatoes from Colorado Potato Beetle. As used herein, the term "plant" is defined as any of various photosynthetic, eukaryotic multicellular organisms of the kingdom Plantae, characteristically producing embryos, containing chloroplasts, having cellulose cell walls, and lacking locomotion. Plants which may be protected by the compositions of the present invention include but are not limited to grain-bearing plants, such as rice, barley and wheat plants; nut-bearing plants, such as pecan and almond trees and peanut plants; fruit-bearing plants such as citrus, banana, strawberry, blackberry and blueberry plants, peach, nectarine, pear and apple trees and grape vines; vegetable plants, such as celery, tomato, corn, potato and pepper plants; trees and, in particular, pine trees, such as the radiata pine and white pine; olive trees; oil palm trees; rubber trees; coffee plants; cotton plants; ornamental plants; flowers; and flowering, bulb producing plants. Preferably, the plants protected by the compositions of the present invention are wheat, pecan, peanut, strawberry, blackberry, blueberry, grape, citrus, banana, peach, nectarine, apple, tomato and coffee plants, flowers and pine trees. As used herein, the term "crop" includes cultivated plant or agricultural produce. Crops may be cultivated for, e.g., food, medical or industrial use. Crops which may be protected by the compositions of the present invention include but are not limited to vegetables, e.g., tomatoes, peppers, corn, potatoes, celery; grains, e.g., rice, barley, wheat; nuts, e.g., almonds, pecans, peanuts; and fruit. Other examples of crops which may be protected by the compositions of the present invention include but are not limited to cacao, sugar cane, sugar beets, coffee beans, rubber latex, cotton and flower bulbs. As used herein, the term "fruit" encompasses an edible, usually sweet and fleshy, ovary of a seed-bearing plant or the spore-bearing structure of a plant that does not bear seeds. As such, fruits are a subclass of plant crops or products. Fruits which may be protected by the molecular iodine of the present invention include but are not limited to grapes, bananas, peaches, nectarines, pears, apples, citrus fruit, such as oranges, grapefruit, tangerines, lemons and limes, and berries, such as strawberries, blackberries and blueberries. As used herein, the term "harvested crop" is defined as any crop which has been removed from the plant from which the crop was derived. Picked fruit and stored grain are examples of harvested crops. Preferably, the harvested crops protected by the compositions of the present invention are wheat, pecans, peanuts, strawberries, blackberries, blueberries, grapes, citrus fruit, bananas, peaches, nectarines, apples, tomatoes, coffee beans, flowers and softwood products, e.g., timber hewn from pine trees. As used herein, the term "agricultural substance" includes plants, crops, harvested crops and mixtures thereof. Optimally, the compositions of the invention comprising molecular iodine are applied at a level readily determined by one of ordinary skill in the art which is sufficient to protect the plants and/or crops, i.e., to prevent substantial damage caused by harmful pests (not necessarily eliminating the pests, however) without itself causing substantial plant or crop damage. The effective amount of molecular iodine applied for plant and/or crop protection is dependant upon a number of factors well known to one of ordinary skill in the art of pesticide application, e.g., upon the type of plant and/or crop, weather conditions, climate, soil and pest(s). In the present invention, the effective amount of molecular iodine applied to plants for protection from pests harmful to such plants, ranges from at least about 0.1 grams per acre of plants to about 10,000 grams per acre of plants, preferably from at least about 0.1 grams per acre to about 100 grams per acre of plants, and most preferably from at least about 1 gram per acre to about 10 grams per acre of plants. The effective amount of molecular iodine applied to harvested crops, for protection of such crops from pests harmful to crops, ranges from at least about 0.01 grams per metric ton of harvested crop to about 5,000 grams per metric ton of harvested crop, preferably from at least about 0.1 grams per metric ton to about 50 grams per metric ton of harvested crop, and most preferably from at least about 1 gram per metric ton to about 10 grams per metric ton of harvested crop. Molecular iodine may either be used alone, e.g. in gaseous form for treating harvested grapes, or may be combined with at least one optional additive before being applied onto plants and/or crops for their protection. The additive may be present, e.g., in the form of an secondary active ingredient. Secondary active ingredients may be, for example, herbicides, fungicides, nematicides, insecticides and fumigants. Preferred secondary active ingredients include but are not limited to the herbicides BACARA and RAFT (available from Rhone Poulenc) , BRONCO, ACCORD and AVADEX (available from Monsanto) ; the fungicides FONGRAL, ARBITRE and SOLITZ (available from Rhone Poulenc) ; the insecticide FIPRONIL (available from Rhone Poulenc) ; and the fumigants chloropicrine, VAPAM and BENSAMID. In a further embodiment, the optional additive may be an inert ingredient. As used herein, the term "inert ingredient" is as defined in 40 C.F.R. § 152.3 (m) (1996), i.e., any substance other than an active ingredient which is intentionally included in a pesticide product. Preferably, the inert ingredient comprises a carrier. In this embodiment, the molecular iodine is added to the carrier before application onto plants and/or crops. This serves three purposes. First, the addition of the molecular iodine to the carrier allows for a small amount of molecular iodine to be distributed over a large surface area. Second, other inert ingredients, which are beneficial to plant and crop protection or growth, can be added to the carrier and distributed along with the molecular iodine. Third, to facilitate application, the protectant composition can be prepared as a concentrate of molecular iodine, and any optional inert ingredient (s) desired, in a carrier and then further diluted before application. The carrier is usually present at the highest percentage level of any of the ingredients present. The carrier may be present in the form of a solid, a liquid or a gas; however, liquid and gaseous carriers are preferred. Preferred gaseous carriers include but are not limited to air, nitrogen, the inert gases (i.e., helium, neon, argon, krypton, xenon and radon) and mixtures thereof. When a liquid carrier is selected, it may be aqueous, organic, inorganic, non-ionic, cationic, anionic, or a mixture, emulsion, or suspension or any combination thereof. Preferred liquid carriers include but are not limited to water, alcohols and oils used in the formulation of agricultural spray emulsions suitable for use on plants and/or crops, and mixtures thereof. Some examples of liquid carriers include nonylphenol; alpha-alkyl-omega- hydroxypoly (oxoethylene) , wherein the alkyl group comprises from 12 to 15 carbon atoms; and the crop oils ORCHEX 796 and ORCHEX 692 made by Esso, an EXXON Company. Inert ingredient (s) other than the carrier may also be present along with the molecular iodine and other optional additive (s). These inert ingredients include but are not limited to fertilizers, fertilizer components, nutrients, micronutrients, promoters (i.e., of molecular iodine activity, such as methyl paraben and propyl paraben) , polyaspartates, bio ass, surfactants, emulsifiers, oils, odorants, waxes, salts, preservatives and iodides. It is desirable that the inert ingredient not comprise an organic acid. As used herein, the term "organic acid" is defined as an aliphatic hydrocarbon compound uninterrupted by heteroatoms, unsubstituted by heteroatoms and unsubstituted by functional groups other than by at least one carboxylic group, i.e., -COOH. Organic acids include monocarboxylic acids, such as the alkanoic acids of molecular formula C a H 2n 0 2 and alkenoic acids of molecular formula C a H 2n . 2 0 2 , dicarboxylic acids, e.g., maleic acid and prostanoic acid, and tricarboxylic acids such as citric acid, but not other derivatives, such as anhydrides and esters, and are further described in the Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, 4:814-869 (1978). While not wishing to be bound by any particular theory, the combination of molecular iodine with a nutrient and/or a micronutrient is thought to enhance the protective effect of the molecular iodine. Preferred inert ingredients, other than carriers, include but are not limited to promoters; plant nutrients, such as nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, boron, chlorine, copper, iron, manganese, molybdenum and zinc; emulsifiers; surfactants, for example, nonylphenol and alkyl polyglycoside oligomers, e.g. , GLUCOPON ® surfactants (available from Henkel) ; and mixtures thereof. Molecular iodine, in the form of any of the embodiments described above, may be applied to plants and/or to crops in the pre-harvest or the post-harvest stage to obtain the desired level of protection from pests. For example, application typically is accomplished by spraying the plants from the ground or from the air. With regard to plant roots, which are generally not exposed to receive atmospheric sprays, application man be made directly or indirectly, e.g., by spraying the surrounding soil with the protectant composition, thus allowing it to penetrate through the soil to reach the roots. Furthermore, applications to plants and/or to crops may be made as many times as necessary per annum to maintain the desired level of protection from pests. The effective amount of molecular iodine applied for each application may vary, as is well known to one of ordinary skill in the art of pesticide application. The plant and/or crop protectant compositions of the present invention may be applied by any convenient method, for example, by using a fixed application system such as a center pivot irrigation system. Preferably, application to fields of plants and/or crops is made by air spraying, i.e., from an airplane or helicopter, or by land spraying. For example, land spraying may be carried out by using a high flotation applicator equipped with a boom, by a back-pack sprayer or by nurse trucks or tanks. Optionally, application may be made to plants which have their fruit(s), vegetable (s) and/or flower (s) protected, e.g., by paper or plastic bags. The following examples are provided to illustrate the preparation of plant and/or crop protectant compositions 5 comprising molecular iodine as the primary active ingredient. The following examples are for the sole purpose of illustration and should not be construed as limiting the scope of the present invention in any sense. 0 Examples The individual components in the following examples are listed as parts by weight. The plant and crop protectant compositions of Examples 1 and 2 are in concentrated form and require the proper 5 dilution as would be readily determinable by one of ordinary skill in this art before application to plants and/or crops. Example 1: Plant and Crop Protectant Composition 1 2.5 parts I 2 , 1.25 parts KI, 10 parts 85% by weight 0 phosphoric acid, 1 part methyl paraben and 1 part propyl paraben are added to a carrier of 32.5 parts alpha-alkyl- omega-hydroxypoly(oxoethylene) , wherein the alkyl group comprises from 12 to 15 carbon atoms, and 54.25 parts water to make 100 parts total of plant and crop protectant 25 composition 1. Example 2: Plant and Crop Protectant Composition 2 25 parts I 2 , 12.5 parts KI, 10 parts methyl paraben, 10 parts propyl paraben, 10 parts magnesium sulfate, 112 parts 30 85% by weight phosphoric acid, 100 parts potassium nitrate, 87.5 parts urea, 2 parts polyvinylpyrrolidone and 25 parts ethylenediamine tetraacetic acid chelated plant microelements (CHAMPION FOLIAR QUELATOS ® available from SQM Nitratos) are added to a carrier of 300 parts nonylphenol and 472 parts 35 water to make 1,166 parts total of plant and crop protectant composition 2. The following examples are illustrations of methods for dilution and application of molecular iodine-containing plant and crop protection compositions formed in accordance with the present invention. Example 3: Application of Plant and Crop Protectant Composition 1 to Grape Plants (pre-harvest) The composition 1 plant and crop protectant solution was diluted as follows prior to application: 0.5 parts composition 1, 5 parts oil (ORCHEX ® ) and 30 parts water. The diluted protectant mixture was applied at a rate of 14 liter per acre to grape plants, to all portions of the plants exposed to the atmosphere, in a pre-harvest stage to protect the plants from Botritis cinerea. The effective molecular iodine coverage was 5.1 grams per acre of grape plants. Selected sections of grape plants were sprayed with a similar solution which differed only in that it contained no I 2 ; these sections were designated as the control group. The solutions were applied at the above rate a total of five times from the time of beginning of flowering to thirty days before harvest. The grape plants sprayed with the composition 1 protectant solution containing molecular iodine showed no sign of disease, in particular Botritis cinerea, unlike the control group which was highly diseased. Example 4: Application of Plant and Crop Protectant Composition 1 to Orange Plants (pre-harvest) The composition 1 plant and crop protectant solution was diluted as follows prior to application: 0.2 parts composition 1 and 1000 parts water. The diluted protectant mixture was applied at a rate of 900 liters per acre to orange trees, primarily to the leaves, fruit and stems, in the pre-harvest stage to protect the plants from Colletotrichum usae and Phytophthora spp. which cause grey rot. The effective molecular iodine coverage was 4.5 grams per acre of orange plants. The protectant mixture was applied at the above rate four times during the pre-harvest period. Water, without composition 1, was applied in the same manner to a control group. The orange plants that were sprayed with the composition 1 protectant solution showed no signs of grey rot, however the orange plants in the control group were severely overtaken with grey rot. Example 5: Application of Plant and Crop Protectant Composition 2 to Banana Plants (pre-harvest) The composition 2 plant and crop protectant solution was diluted as follows prior to application: 0.25 parts composition 2, 0.12 parts emulsifier (the nonionic emulsifier TRITON X-45 ® available from Rohm & Haas) , 12 parts oil (ORCHEX ® ) and 3 parts water. The diluted protectant mixture was applied at a rate of 6.0 liters per acre to the leaves and stems of banana plants in a pre-harvest stage to protect the plants from the foliar fungal disease black sigatoka, which is caused by Mycosphaerella musicola and Mycosphaerella fijiensis. During the application, any developing banana clusters were covered with bags before application of the diluted protectant 2. The effective molecular iodine coverage was 2.53 grams per acre of banana plants. Selected sections of banana plants were sprayed with a similar solution, the control composition, which differed only in that it contained no I 2 ; these sections were designated as the control group. The protectant and control compositions were applied at the above rate to the banana plants, before and after flowering, every 15 days during the rainy season and every 21 days during the dry season. The banana plants sprayed with the solution of protectant 2, containing molecular iodine, showed no sign of infection by the foliar fungal disease black sigatoka. However, the banana plants in the control group were severely infested with black sigatoka. Example 6: Application of Plant and Crop Protectant Composition 1 to Harvested Bananas (post-harvest) The composition 1 plant and crop protectant solution was diluted as follows prior to application: 0.1 parts composition 1 and 20 parts water. The mixture was applied once, at the rate of 22 liters per metric ton, to harvested bananas for protection against crown rot caused by Verticillium theabro ae, Gloeosporium musarum and Fusarium. The effective amount of molecular iodine applied was 2.8 grams per metric ton of bananas. Control groups were sprayed with a similar solution which differed only in that it contained no I 2 . After an average of two weeks, the control groups of bananas displayed signs of crown rot however the bananas sprayed with the protectant solution 1, containing molecular iodine, were free of crown rot. While the present invention has been described with reference to preferred embodiments and illustrative examples, it should be understood that one of ordinary skill in the art, after reading the foregoing specification, would be able to effect various changes, substitutions of equivalents and modifications to the methods and compositions described herein. Therefore, it is intended that the scope of the invention not be limited by reference to the illustrative examples. Rather, the scope of the present invention should be construed with reference to the accompanying claims.

Claims: CLAIMS What is claimed is: 1. A method for protecting an agricultural substance from pests which are harmful to the agricultural substance, said method comprising: selecting a composition which comprises molecular iodine or which, upon application, releases molecular iodine; and applying the composition to the agricultural substance as many times as necessary per annum in an amount effective to prevent substantial damage to the agricultural substance from said pests. 2. The method of claim 1, further comprising selecting the agricultural substance from the group consisting of crops, harvested crops and mixtures thereof. 3. The method of claim 1, further comprising applying the composition by spraying. 4. The method of claim 1, further comprising selecting plants as the agricultural substance, and applying a sufficient amount of the composition to said plants so as to result in the application of from at least about 0.1 grams of molecular iodine per acre of plants to about 10,000 grams of molecular iodine per acre of plants. 5. The method of claim 4, further comprising covering at least one portion of said plants selected from the group consisting of fruits, vegetables and flowers before applying the composition to prevent contact with the composition. 6. The method of claim 4 , further comprising choosing the plant from the group consisting of wheat, pecan, peanut, strawberry, blackberry, blueberry, grape, citrus, banana, peach, nectarine, apple, tomato and coffee plants, flowers and pine trees. 7. The method of claim 4, further comprising applying a sufficient amount of the composition to said plants so as to result in the application of from at least about 0.1 grams of molecular iodine per acre of plants to about 100 grams of molecular iodine per acre of plants. 8. The method of claim 7, further comprising applying a sufficient amount of the composition to said plants so as to result in the application of from at least about 1 gram of molecular iodine per acre of plants to about 10 grams of molecular iodine per acre of plants. 9. The method of claim 1, further comprising selecting harvested crops as the agricultural substance, and applying a sufficient amount of the composition to said harvested crops so as to result in the application of from at least about 0.01 grams of molecular iodine per metric ton of harvested crops to about 5,000 grams of molecular iodine per metric ton of harvested crops. 10. The method of claim 9, further comprising choosing the harvested crop from the group consisting of wheat, pecans, peanuts, strawberries, blackberries, blueberries, grapes, citrus, bananas, peaches, nectarines, apples, tomatoes, coffee beans, flowers and softwood products. 11. The method of claim 9, further comprising applying a sufficient amount of the composition to said harvested crops so as to result in the application of from at least about 0.1 grams of molecular iodine per metric ton of harvested crops to about 50 grams of molecular iodine per metric ton of harvested crops. 12. The method of claim 11, further comprising applying a sufficient amount of the composition to said harvested crops so as to result in the application of from at least about 1 gram of molecular iodine per metric ton of harvested crops to about 10 grams of molecular iodine per metric ton of harvested crops. 13. The method of claim l, further comprising adding at 5 least one additive to the composition, the additive selected from the group consisting of secondary active ingredients and inert ingredients, with the proviso that the additive is not an organic acid. 10 14. The method of claim 13 , further comprising selecting the secondary active ingredient from the group consisting of herbicides, fungicides, nematicides, insecticides and fumigants. 15 15. The method of claim 13 , further comprising selecting the inert ingredient from the group consisting of carriers, fertilizers, fertilizer components, nutrients, micronutrients, promoters, polyaspartates, biomass, surfactants, emulsifiers, oils, odorants, waxes, salts, 20 preservatives and iodides. 16. The method of claim 15, further comprising selecting the inert ingredient from the group consisting of methyl paraben, propyl paraben, nitrogen, phosphorus, potassium, calcium, 25 magnesium, sulfur, boron, chlorine, copper, iron, manganese, molybdenum, zinc, nonylphenol, alkyl polyglycoside oligomers and mixtures thereof. 17. The method of claim 13, further comprising selecting the 30 inert ingredient to be a liquid carrier. 18. The method of claim 17, further comprising selecting the liquid carrier from the group consisting of water, alcohols, oils used in the formulation of agricultural spray emulsions 35 and mixtures thereof. 19. The method of claim 13, further comprising selecting the inert ingredient to be a gaseous carrier. 20. The method of claim 19, further comprising selecting the gaseous carrier from the group consisting of air, nitrogen, the inert gases and mixtures thereof. 21. A method for protecting an agricultural substance selected from the group consisting of plants, crops, harvested crops and mixtures thereof, from pests which are harmful to the agricultural substance comprising: selecting a composition which comprises molecular iodine or which, upon application, releases molecular iodine and at least one additive selected from the group consisting of secondary active ingredients and inert ingredients, with the proviso that the additive is not an organic acid; and applying the composition to the agricultural substance as many times as necessary per annum in an amount effective to prevent substantial damage to the agricultural substance from said pests. 22. A protectant composition for agricultural substances which comprises molecular iodine or which, upon application, releases molecular iodine. 23. The protectant composition of claim 22, which further comprises at least one additive selected from the group consisting of secondary active ingredients and inert ingredients, with the proviso that the additive is not an organic acid. 24. The protectant composition of claim 23, wherein the additive further comprises at least one secondary active ingredient selected from the group consisting of herbicides, fungicides, nematicides, insecticides and fumigants. 25. The protectant composition of claim 23, wherein the additive further comprises at least one inert ingredient selected from the group consisting of carriers, fertilizers, fertilizer components, nutrients, micronutrients, promoters, 5 polyaspartates, biomass, surfactants, emulsifiers, oils, odorants, waxes, salts, preservatives and iodides. 26. The protectant composition of claim 25, wherein the inert ingredient is selected from the group consisting of 0 methyl paraben, propyl paraben, nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, boron, chlorine, copper, iron, manganese, molybdenum, zinc, nonylphenol, alkyl polyglycoside oligomers and mixtures thereof. 5 27. The protectant composition of claim 23 which further comprises a liquid carrier. 28. The protectant composition of claim 27, wherein the liquid carrier is selected from the group consisting of 0 water, alcohols, oils used in the formulation of agricultural spray emulsions and mixtures thereof. 29. The protectant composition of claim 23 which further comprises a gaseous carrier. 5 30. The protectant composition of claim 29, wherein the gaseous carrier is selected from the group consisting of air, nitrogen, the inert gases and mixtures thereof. 30 31. A protectant composition for agricultural substances which comprises molecular iodine or which, upon application, releases molecular iodine and at least one additive selected from the group consisting of secondary active ingredients and inert ingredients, with the proviso that the additive is not 35 an organic acid.

Inventors: BASINGER WILLIAM H, GONZALEZ RODRIGO J, NARITELLI HUGO R, OBER ALFONSO G, BASINGER, WILLIAM, H., GONZALEZ, RODRIGO, J., NARITELLI, HUGO, R., OBER, ALFONSO, G.
Applicants: AJAY NORTH AMERICA, SQM IODO S A, SQM IODO S.A.
Application year: 1998
Main classification: A01N59
IPC codes: A01N59