WO2005027617A2 - Compositions d'engrais pour plantes contenant des sels de phosphate et de phosphonate, des chelates de metal, et des derives correspondants - Google Patents

Compositions d'engrais pour plantes contenant des sels de phosphate et de phosphonate, des chelates de metal, et des derives correspondants Download PDF

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Publication number
WO2005027617A2
WO2005027617A2 PCT/US2004/030507 US2004030507W WO2005027617A2 WO 2005027617 A2 WO2005027617 A2 WO 2005027617A2 US 2004030507 W US2004030507 W US 2004030507W WO 2005027617 A2 WO2005027617 A2 WO 2005027617A2
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metal
composition
group
aqueous solution
salt
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PCT/US2004/030507
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English (en)
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WO2005027617A3 (fr
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John B. Taylor
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Foliar Nutrients, Inc.
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Priority claimed from US10/017,687 external-priority patent/US20020193351A1/en
Application filed by Foliar Nutrients, Inc. filed Critical Foliar Nutrients, Inc.
Publication of WO2005027617A2 publication Critical patent/WO2005027617A2/fr
Publication of WO2005027617A3 publication Critical patent/WO2005027617A3/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/26—Phosphorus; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal

Definitions

  • Patent No. 6,338,860 which is a continuation-in-part of U.S. Patent 5,997,910, which is a divisional of U.S. Patent 5,800,837, which is a continuation-in-part of U.S. Patent 5,736,164. All of the aforementioned applications and patents are incorporated herein by reference.
  • the present invention is broadly concerned with compositions and methods of use that provide improved efficacy in fertilizing and controlling fungus and bacterial infections in plants. More particularly, the compositions and methods relate to heavy metal chelates, and preferably to a copper chelate in the form of Cu-EDDHA (copper ethylenediamine-di- o-hydroxyphenylacetic acid), including an amount of phosphate (PO4) and phosphonate (PO3), in aqueous solution.
  • Fungicides as well as bactericides, are either chemical or biological agents used to protect agricultural crops from infectious pathogens which, if left uncontrolled, result in the weakening or destruction of a plant. In regards to agricultural crops, this is unacceptable, as economic losses will result.
  • Specific pathogens which tend to have an undesired effect on various agricultural crops include Citrus Greasy Spot, Citrus Melanose, Oak Leaf Blister, Erwinia, Xanthomonas, and Alternaria.
  • it is desired to have a fungicide and bactericide composition that readily eliminates or treats these various plant maladies, as well as other infectious agents.
  • Copper (Cu) compounds that are active as fungicides and bactericides have been in agricultural use since the advent of Bordeaux in the grape vineyards of France in the early 1800s. It has been observed that various types of copper compounds can be used to effectively treat various plant pathogens. As such, many different formulations of fungicides employing copper compounds, such as wettable powders, water based flowables, and dry flowables, are commonly used today in modern agricultural applications. While copper compounds are known to impart desirable fungicidal and bactericidal properties, there are associated problems. Specifically, known copper compounds are typically either phytotoxic, non-soluble, or ineffective as a fungicide or bactericide.
  • copper compounds used as fungicides have, for the most part, been inorganic in form when applied to agricultural uses.
  • the inorganic copper compounds have been used because they have been observed to be non-phytotoxic.
  • Organic forms of the copper compounds, while beneficially water soluble, have been found to be generally phytotoxic, especially in foliar applications.
  • Water soluble, copper compounds such as CuSO4, though effective to inhibit germination of fungus spores, cannot be used in foliar applications to agricultural crops because the cupric ion is extremely phytotoxic. Therefore, relatively insoluble forms of inorganic copper compounds, such as cupric hydroxide, have been found to be more effective fungicides.
  • Modern day agricultural uses of inorganic copper compounds as fungicides employ varying forms of copper compounds having relatively low water solubility and include, for example, cupric hydroxide, tri basic copper sulfate, and tank mix combinations (with heavy metal ethylene-bis-di-thiocarbamate fungicides to enhance the bactericidal activity against certain important agricultural bacterial such as Xanthomonas, Pseudomonas, and Erwinia).
  • the lack of solubility of the inorganic copper compounds is an undesired problem. Because known and popular copper fungicides are largely water insoluble, they are normally applied in relatively large volume aqueous suspensions and, as such, are readily removed by rain after application.
  • Inorganic copper compounds alone are also not particularly effective in treating certain forms of fungus known as Phytophthora. From 1845 to 1846, the Irish Potato Famine occurred, which was one of the most devastating crop failures in the history of the world. The potato famine was caused by the disease late blight which resulted in harvested potatoes quickly decaying, making them unsuitable for consumption. The disease is also known to cause defoliation in infected plants. Late blight is caused by a Phytophthora organism infecting a potato or tomato plant.
  • the Phytophthora organism if not controlled, can cause major economic damage to agricultural crops, with the resulting damage causing the loss of millions of dollars in crop revenues. Additionally, there is the possibility of significant reduction of the potato and tomato supply available to consumers. [0010] To control late blight, it has been recommended that the contaminated potatoes and/or tomatoes be buried in deep pits and covered by at least two feet of soil. In Northern Latitudes, the potatoes or tomatoes can be spread on the soil surface and allowed to freeze during the winter. These methods temporarily prevent the spread of the disease, but do not prevent infection and attack by the Phytophthora infestans. The treatment only addresses plants and crops after they have been destroyed.
  • compositions or methods that can be administered to potato and tomato fields to actively control and prevent the spread of the Phytophthora infestans infestation.
  • Some species of the Phytophthora genus can be controlled, such as Phytophthora parasitica.
  • fosetyl-al (ethyl phosphonate) can be administered to plants to control diseases such as root rot caused by Phytophthora parasitica.
  • PO3 compositions are highly effective in combating the disease root rot and, in particular, some of the species of the genus Phytophthora.
  • Phosphorus is an essential element in plant nutrition because it governs the energy producing reactions, including those that are oxidative and photo phosphorylative. Phosphorous is essential to the production of adenosine diphosphate (ADP) and adenosine triphosphate (ATP). Energy-rich phosphate bonds of ADP and ATP provide the energy for many of the physiological reactions that occur in plants.
  • ADP adenosine diphosphate
  • ATP adenosine triphosphate
  • phosphonate sometimes also referred to as "phosphite”
  • Phosphonic and phosphorous acids have the formula H3PO3 and a molecular weight of 82.00. Their structures from the International Union of Pure and Applied Chemistry are shown below: OH OH
  • phosphate means the salts (organic or inorganic) of phosphoric acid having the formula H3PO4, molecular weight of 98.00 and having the following structure: O
  • phosphonate (PO3) alone is typically considered an unacceptable source of phosphorus (P) for plants. It is known that PO3 must be converted to PO4 to be utilized by a plant.
  • PO3 must be converted to PO4 to be utilized by a plant.
  • phosphonates (PO3) have been shown to enhance the plant's phytoimmune system. The phosphonate induced stimulation of the phytoimmune system is triggered by the induction of ethylene production, followed by a rapid accumulation of phytoalexins at the site of infection. Phytoalexins are antibiotics which result from the interaction between the host plant and a pathogen. The phytoalexins are synthesized by and accumulate in the plant to inhibit the pathogen.
  • phosphates (PO4) were not viewed as a solution to pathological acerbation of fungal infections or infections produced by other genuses. This is because phosphates (PO4) are viewed primarily as a fertilizer with only limited, or even detrimental, phytoimmune properties.
  • U.S. Patent 5,514,200 teaches that phosphate fertilizers inhibit beneficial symbiosis between plant roots and mycorrhizal fungi, and further promote bacterial and fungical growth in the rhizosphere, including the growth of pathogenic fungi and other small soil-borne organisms.
  • Phosphates (PO4) have also been considered to be a competitive inhibitor for phosphonate assimilation, thus inhibiting the ability of phosphonates (PO3) to protect against fungus attack. See, Pegg, K.G. and deBoer, R.F., "Proceedings of the Phosphonic (Phosphorous) Acid Work Shop," Australiasian Plant Pathology, Vol. 19 (4), pp. 117 and 144, 1990. Yet further, phosphonates (PO3) and phosphates (PO4) were believed to be "biological strangers," with the presence of phosphonates (PO3) or esters of phosphonates, exerting little or no influence on enzyme reactions involving phosphates.
  • the requirements for a successful phosphonate-based fungicide depend on the promotion of the phosphonate-induced pathological acerbation of fungical or other genus infections. More particularly, it is desired to have a composition and/or method that prevents Phytophthora infestans infection and destruction of plants.
  • the present invention relates to a heavy metal chelate fungicide and bactericide composition and methods of using the composition.
  • the chelate is a composition that is a member of the EDDHA (ethylenediamine-di- o-hydroxyphenylacetic acid) family, and the metal is selected from the group consisting of iron, copper, manganese, zinc, nickel, tin, and combinations thereof. Copper, however, is the most preferred metal.
  • the present invention addresses the problems discussed before, of solubility, phytotoxicity, and effectiveness.
  • the heavy metal chelate fungicide and bactericide composition provides an improved antifungal and antibacterial composition for use on plants that contains, as active ingredients, fungicidally and bactericidally effective amounts of the heavy metal chelates in aqueous solution. It has been observed that the application of the heavy metal chelate composition to a plant substantially eliminates fungus and bacteria disease. Not only is the composition effective in eliminating fungus and bacteria, but it is substantially non-phytotoxic. Also, the heavy metal chelate is soluble in aqueous solution. Thus, the composition provides for protection of plants against fungal and bacterial infections without the attendant phytotoxicity.
  • the heavy metal chelate composition is a singular product that imparts antifungal and antibacterial protection upon application without being excessively phytotoxic.
  • the heavy metal chelate composition is, additionally, environmentally safe, comparatively inexpensive to use, and has low mammalian toxicity.
  • the present antifungal and bacterial composition is comprised of an active material, a fungicidally effective amount of a heavy metal chelate, and an agriculturally acceptable carrier, such as water.
  • the preferred fungicidal and bactericidal compositions is comprised of water and a heavy metal chelate selected from the group consisting of Fe-EDDHA (iron ethylenediamine- di-o-hydroxyphenylacetic acid), Cu-EDDHA, Mn-EDDHA, Zn-EDDHA, Sn-EDDHA, and mixtures thereof.
  • a heavy metal chelate selected from the group consisting of Fe-EDDHA (iron ethylenediamine- di-o-hydroxyphenylacetic acid), Cu-EDDHA, Mn-EDDHA, Zn-EDDHA, Sn-EDDHA, and mixtures thereof.
  • Other family members of EDDHA can be substituted therefor, including pEDDHA and EDDHMA.
  • both antifungal and antibacterial effects are achieved with one composition, as well as fertilizer effects.
  • the composition also includes phosphate (PO4) and phosphonate (P03 ) constituents which, when combined, provide for a synergistic effect that results in the substantial protection against infection of plants by Phytophthora, especially Phytophthora infestans.
  • PO4 phosphate
  • P03 phosphonate
  • the phosphate and phosphonate constituents can be combined to form a composition, which can be applied to plants, especially tomatoes and potatoes, to prevent infection by Phytophthora infestans and diseases caused by such infection.
  • Application can be achieved by using either a dry mix or an aqueous solution.
  • the preferred composition for preventing Phytophthora will be comprised of potassium phosphonate and potassium phosphate, as it has been found that these two constituents, when combined, will cause a synergistic effect which results in the substantial prevention of infection by Phytophthora. It is believed, that the rate by which infection is prevented is increased by at least 100% when the two constituents are combined, as compared to the additive effect of the combined salts.
  • the two constituents will be combined in an amount sufficient to prevent infection and manifestation by various disease causing organisms, with the particular amounts combined dependent upon the particular species of plant to be treated, the specific disease causing organism to be treated, and the particular phosphate salt and phosphonate salt that will be combined.
  • the composition should be applied at least once to the plants to be treated. While one application is sufficient, it is typically preferred to make multiple applications. Essentially, any plant infected by Phytophthora can be treated, with it most preferred to apply the composition to potato and tomato plants. It should also be noted that the composition not only inhibits Phytophthora, but is environmentally safe, inexpensive to use, and has low mammalian toxicity.
  • Phosphonate salts useful in the practice of the invention also include those organic and inorganic salts taught by U.S. Patent Nos. 4,075,324 and 4,119,724 to Thizy et al., (see, e.g., col. 1, In. 51-69 through col. 2, In. 1-4).
  • the present invention in another aspect, also has been found to be effective as a growth stimulator or fertilizer for plants, and addresses the problems in the art with regard to finding effective fertilizers.
  • the present invention provides a means for applying a single product to plants which is both an effective fungicide and an effective fertilizer.
  • a further object of this aspect of the invention is to function as a fertilizer which provides substantial growth response results.
  • Another object of this aspect of the invention is to function as a fertilizer which is ecologically and human compatible, is economical, and is efficient.
  • the present invention relates to a composition that is both a fungicide and a bactericide and a method for using such composition.
  • the composition is advantageously useful in eliminating or at least substantially reducing the effects of infection by various fungal and bacterial plant pathogens.
  • the composition is a heavy metal chelate in aqueous solution, with it preferred that the chelate be a member of the EDDHA family of compositions.
  • the heavy metal attached to the chelate can be selected from any of a variety of row 4 or 5 metal constituents.
  • the present composition is comprised of a heavy metal chelate and an amount of water to form an aqueous composition.
  • the heavy metal chelate can be formed by a known process, with the reaction summarized as reacting an amount of metal chloride hexahydrate with water and an amount of mono-amide di-hydrochloride in a reaction vessel.
  • a catalyst such as sodium hydroxide, is then added which will cause formation of the metal oxide EDDHA.
  • the metal hexahydrates that can be reacted with the mono-amide di-hydrochloride are iron, zinc, nickel, tin, manganese, and copper.
  • the resulting heavy metal chelates that are suitable for use include: Fe-EDDHA, Cu-EDDHA, Zn-EDDHA, Mn-EDDHA, Sn-EDDHA, and combinations thereof.
  • the term "heavy metal chelate” refers to an organic coordination "complexing" compound in which a metal ion is bound to atoms of non-metals, e.g., nitrogen, carbon, or oxygen, to form a hetrocylic ring having coordinate covalent bounds.
  • the non-metal atoms may be attached to the metal ions by from one to six linkages and, thus, are called uni, bi, tri dentate, etc., meaning 1-, 2-, or 3-tooth.
  • Heavy metals such including cobalt, copper, iron, nickel, zinc, nickel, tin, magnesium, and platinum, are the metal ions commonly involved in chelate structures.
  • Examples of specific heavy metal chelate structures include: [0036] Fe-HEEDTA (hydroxyethylethylenediaminetriacetic acid), Fe-EDTA (ethylenediaminetetraacetic acid), Fe-DTPA (di-ethylenetriaminepentaacetic acid), Fe-EDDHA
  • the heavy metal chelate aqueous composition will be mixed with an amount of aqueous solution. Generally, special treatment of the water is not required, such as deionizing the water for example. Additionally, the mixing will preferably occur under ambient conditions. The heavy metal chelate will be mixed into the water in an amount sufficient to cause the finished composition to equal from about 0.01 pounds to about 2.0 pounds of Al per acre.
  • the heavy metal chelate will equal between 0.01 and 0.05 pounds of Al per acre. Typically this means adding the heavy metal chelate to the water in an amount equal to between about 1% and about 5% by weight of the total solution. More preferably, the heavy metal chelate will be added in an amount equal to about 3% by weight of the total solution.
  • the present antifungal and bacterial composition is comprised of an active material, a fungicidally effective amount of a heavy metal chelate, and an agriculturally acceptable carrier, such as water.
  • the preferred fungicidal and bactericidal compositions is comprised of water and a heavy metal chelate selected from the group consisting of Fe-EDDHA (iron ethylenediamine- di-o-hydroxyphenylacetic acid), Cu-EDDHA, Mn-EDDHA, Zn-EDDHA, Sn-EDDHA, and mixtures thereof.
  • a heavy metal chelate selected from the group consisting of Fe-EDDHA (iron ethylenediamine- di-o-hydroxyphenylacetic acid), Cu-EDDHA, Mn-EDDHA, Zn-EDDHA, Sn-EDDHA, and mixtures thereof.
  • Other family members of EDDHA can be substituted therefor, including pEDDHA and EDDHMA.
  • both antifungal and antibacterial effects are achieved with one composition, as well as fertilizer effects.
  • the composition also includes phosphate (PO4) and phosphonate
  • the phosphate and phosphonate constituents can be combined to form a composition, which can be applied to plants, especially tomatoes and potatoes, to prevent infection by Phytophthora infestans and diseases caused by such infection.
  • Application can be achieved by using either a dry mix or an aqueous solution.
  • the preferred composition for preventing Phytophthora will be comprised of potassium phosphonate and potassium phosphate, as it has been found that these two constituents, when combined, will cause a synergistic effect which results in the substantial prevention of infection by Phytophthora. It is believed, that the rate by which infection is prevented is increased by at least 100% when the two constituents are combined, as compared to the additive effect of the combined salts.
  • the two constituents will be combined in an amount sufficient to prevent infection and manifestation by various disease causing organisms, with the particular amounts combined dependent upon the particular species of plant to be treated, the specific disease causing organism to be treated, and the particular phosphate salt and phosphonate salt that will be combined.
  • Variations of the phosphate and phosphonate constituents can be used. As such, it is particularly preferred if the the compound comprises an effective amount of at least one first salt having the following formula : R 2
  • At least one second salt selected from compounds having the formula:
  • Ri is selected from the group consisting of H, K, an alkyl radical containing from 1 to 4 carbon atoms, halogen-substituted alkyl or / nitro-substituted alkyl radical, an alkenyl, halogen-substituted alkenyl, alkynl, halogen-substituted alkynl, alkoxy-substituted alkyl radical, ammonium substituted by alkyl or hydroxy alkyl radicals; R 2 and R 3 are selected from the group consisting of H and K; Me is selected from the group consisting of K, alkaline earth metal cations, an aluminum atom, and an ammonium cation; n is a whole number equal to between 1 and 3, equal to the valence of Me; and at least one metal chelate wherein said metal is a metal selected from rows 4 or 5 of the periodic table of the elements.
  • the aqueous composition is then ready for application to plants, in particular agricultural crops.
  • the aqueous composition is typically easily applied by spraying or other means of distributing the aqueous solution in a sufficient amount to the plants.
  • the heavy metal chelate must be applied in a sufficient Al amount, without resulting in phytotoxicity. Unacceptably high levels of phytotoxicity result in foliar burn, defoliation and stem die-back, necrosis, plant stunting, or death. Phytotoxicity can be rated on an international scale of 0-10 where 0 is equal to no phytotoxicity and 10 is complete death of the plant.
  • the heavy metal chelate is applied in an amount so that the phytotoxicity is equal to between 0 and 5.
  • Phytotoxicity rankings of Fe chelates used in foliar applications are as follows: Fe-HEEDTA ⁇ most phytotoxic; Fe-EDTA — intermediate phytotoxic, Fe-DTPA ⁇ less phytotoxic, and Fe-EDDHA — least phytotoxic.
  • the Fe-EDDHA is preferred because it is the least phytotoxic while still imparting excellent fungicidal and bactericidal properties.
  • Heavy metal chelates disclosed herein will have a water solubility acceptable for use in the inventive fungicide and bactericide.
  • solubility of sequestrene 138 Fe Iron Chelate in pounds per 100 gallons of water, at various temperatures is similar to the present heavy metal chelate in aqueous solution.
  • Solubility weight/100 gals. H2O is shown in Table 1 below: TEMPERATURE (°C) LBS Oz. 0 69 11 10 70 7 20 75 4 30 81 11 40 84 1 50 88 1
  • Sequestrene 138 Fe contains 6% Iron as metallic, or 8.5% iron as Fe2 ⁇ 3-
  • the commercial product has a moisture content of not more than 10%.
  • this is exemplary of a suitable solubility.
  • the heavy metal chelate, in particular the Cu-EDDHA to have a solubility of about 100% where at least 80 Ibs.of heavy metal chelate is dissolved in 100 gallons of H 2 O at 50° C.
  • heavy metal chelation generally increases the water solubility of the heavy metal ion and the availability in certain soil conditions of the metal ion where calcareous and high pH situations would otherwise prevent metal ions from being available to the plant as a fungicide.
  • the preferable method of application is foliar, either by ground or aerial equipment, but is not limited to that method alone. Injection or soil applications, for example, can also be used depending upon the specific crops and pathogens.
  • compositions and method relate to heavy metal chelates, and preferably a copper chelate in the form of Cu-EDDHA (copper sodium cupric ethylenediamine-di-o-hydroxyphenylacetic acid), in an aqueous solution, also including an effective amount of phosphate (PO4 ) and phosphanate (PO3), which fulfills all the objects and advantages sought therefore.
  • Cu-EDDHA copper sodium cupric ethylenediamine-di-o-hydroxyphenylacetic acid
  • PO3 phosphanate

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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Abstract

L'invention concerne des compositions et des procédés permettant d'améliorer l'efficacité des engrais et de lutter contre les infections fongiques et bactériennes chez les plantes, et plus précisément en rapport avec des chélates de métaux lourds, et de préférence un chélate de cuivre sous la forme de Cu-EDDHA (éthylènediamine de cuivre-acide di-o-hydroxyphénylacétique), y compris une quantité de phosphate (P04) et de phosphonate (P03), en solution aqueuse.
PCT/US2004/030507 2001-10-30 2004-09-16 Compositions d'engrais pour plantes contenant des sels de phosphate et de phosphonate, des chelates de metal, et des derives correspondants WO2005027617A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/017,687 US20020193351A1 (en) 1996-08-30 2001-10-30 Fungicidal and bactericidal compositions for plants containing phosphonate and phosphate salts, metal chelates, and derivatives thereof
US50325503P 2003-09-16 2003-09-16
US60/503,255 2003-09-16

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WO2005027617A2 true WO2005027617A2 (fr) 2005-03-31
WO2005027617A3 WO2005027617A3 (fr) 2005-10-13

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5800837A (en) * 1996-08-30 1998-09-01 Foliar Nutrients, Inc. Plant fertilizer compositions containing phosphonate and phosphate salts and derivatives thereof
WO2002056680A2 (fr) * 2000-10-31 2002-07-25 Foliar Nutrients, Inc. Compositions fongicides et bacteriennes destinees a des plantes contenant des sels de phosphonate et de phosphate, des chelates de metal et leurs derives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5800837A (en) * 1996-08-30 1998-09-01 Foliar Nutrients, Inc. Plant fertilizer compositions containing phosphonate and phosphate salts and derivatives thereof
WO2002056680A2 (fr) * 2000-10-31 2002-07-25 Foliar Nutrients, Inc. Compositions fongicides et bacteriennes destinees a des plantes contenant des sels de phosphonate et de phosphate, des chelates de metal et leurs derives

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