WO2007023481A1 - Compositions biocides non phytotoxiques destinee a un usage agricole et veterinaire - Google Patents

Compositions biocides non phytotoxiques destinee a un usage agricole et veterinaire Download PDF

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Publication number
WO2007023481A1
WO2007023481A1 PCT/IL2005/000917 IL2005000917W WO2007023481A1 WO 2007023481 A1 WO2007023481 A1 WO 2007023481A1 IL 2005000917 W IL2005000917 W IL 2005000917W WO 2007023481 A1 WO2007023481 A1 WO 2007023481A1
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Prior art keywords
composition
aqueous solution
composition according
acid
soil
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PCT/IL2005/000917
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English (en)
Inventor
Joshua Gad-El
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A. Shitzer Ltd.
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Priority to PCT/IL2005/000917 priority Critical patent/WO2007023481A1/fr
Publication of WO2007023481A1 publication Critical patent/WO2007023481A1/fr
Priority to IL189745A priority patent/IL189745A0/en

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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
    • A01N59/08—Alkali metal chlorides; Alkaline earth metal chlorides

Definitions

  • the present invention relates to non-phytotoxic biocidal agricultural and veterinary compositions, in particular compositions effective in soil pre-planting sanitation and treatment of seeds, plants and produce.
  • Soil disinfestation is a standard procedure among crop growers in agriculture industry and in large scale home gardening.
  • the disinfestation process is directed to the extermination of soil-borne pests such as bacteria, nematodes, fungi, viruses, protozoa, mycoplasmas and insects at different growth stages, etc., in an attempt to increase the soil's productivity and to prevent diseases from damaging or reducing agricultural yield.
  • Methyl bromide was the most widely used and most effective broad-spectrum soil fumigant available. In 1993, methyl bromide was listed as an ozone-depleting compound and has been phased out of use in the USA by the Clean Air Act of 1990. Alternative compositions used for soil disinfestation are not as effective as methyl bromide in eradicating a wide range of soil-borne pathogens and novel compositions are sought.
  • Halides such as hypochlorites (e.g. liquid sodium hypochlorite, calcium hypochlorite), trichlorocyanuric acid and n-chloro-para-toluene sulfonamide sodium salt (Chloramine ® T) are known as bleaching and sanitizing agents for domestic, industrial and to a lesser extent, agricultural use.
  • hypochlorites e.g. liquid sodium hypochlorite, calcium hypochlorite
  • trichlorocyanuric acid and n-chloro-para-toluene sulfonamide sodium salt Chloramine ® T
  • Chloramine ® T n-chloro-para-toluene sulfonamide sodium salt
  • the halides suffer from several drawbacks.
  • the liquid products are corrosive, unstable and readily inactivated by organic matter, thus limiting their utility and reliability, particularly on farms where large quantities of organic matter are encountered.
  • the solid products are more stable but are much less reactive.
  • Chloramine ® T for example, requires extremely high concentrations to produce an acceptable biocidal effect, and exhibits reduced activity in the presence of organic matter.
  • EP 0 158 508 discloses an adjustable strength laundry aid package comprising two components, a bleach base composition and a bleach activator.
  • the bleach base composition includes an oxygen-bleaching agent for use in fabric laundering while the bleach activator composition includes a halide salt or salts selected from the group consisting of chloride salts and bromide salts of an alkali metal or metals. That invention is exemplified by compositions comprising at least 50% halide salt(s).
  • the components are packaged separately to control activation of the bleach at the time of fabric laundering.
  • ZA 9701266 discloses a composition for the sanitation of water comprising a disinfecting component selected from sodium bromide, potassium bromide, ammonium bromide, potassium iodide, sodium iodide, trichloroisocyanurate, sodium chloride or a combination thereof, and an activator component, the activator component being an oxidizing agent.
  • a disinfecting component selected from sodium bromide, potassium bromide, ammonium bromide, potassium iodide, sodium iodide, trichloroisocyanurate, sodium chloride or a combination thereof
  • an activator component being an oxidizing agent.
  • U.S. Patent No. 3,337,466 discloses effervescent compositions for cleaning dentures comprising a mixture of from about 5 to about 40 parts of a mixture of potassium monopersulfate, potassium sulfate and potassium hydrogen sulfate (Oxone®); from about 40 to about 5 parts of an inorganic water soluble peroxide of a Group I or II metal; up to about 5 parts of a water soluble halide selected from chloride, bromide and iodide of an alkali or alkaline earth metal and of ammonium; from about 15 to about 85 parts of a water-soluble inorganic alkaline filler; a chelating agent and a wetting agent.
  • the '466 patent discloses that an aqueous solution derived from the composition has a pH of least 7.
  • a composition comprising a plurality of water- soluble halides is neither taught nor suggested in that patent.
  • U.S. Patent No. 4,822,512 discloses disinfecting, particularly virucidal, compositions comprising 0.01 to 5 parts by weight of a total of 100 parts of an inorganic halide, preferably sodium chloride; an oxidizing agent which, in aqueous solution, reacts with the halide to generate hypohalite ions; sulfamic acid; an optional non-reducing organic acid and an anhydrous alkali metal phosphate.
  • the '512 patent demonstrates the use of a composition comprising sodium chloride for veterinarian applications and water sanitation, for example in livestock and fishery farms.
  • the '512 patent neither teaches nor suggests a composition comprising a plurality of inorganic halides nor the use of the compositions in soil sanitization or seed disinfection.
  • a need for improved halide-based biocidal compositions for use in agricultural applications Specifically, the need exists for non-phytotoxic formulations effective for soil disinfestation both prior to seeding and during cultivation.
  • the present invention is directed to novel non-phytotoxic biocidal/antimicrobial compositions and methods of use thereof.
  • the present invention is based on the unexpected discovery that a composition comprising a mixture of two or more inorganic halides possesses increased biocidal activity when compared to a composition comprising a single inorganic halide.
  • the biocidal compositions of the invention comprise novel combinations of known ingredients that show an unexpected synergistic effect compared to hitherto known compositions.
  • compositions have utility in agricultural applications, in particular in agronomic and veterinary applications.
  • the present invention provides a dry, water-soluble, non-phytotoxic biocidal composition comprising:
  • composition comprising a mixture of two or more inorganic halides.
  • This effect is evidenced in experiments comparing the composition of the present invention to a similar composition comprising a single halide.
  • the present invention provides a composition comprising:
  • composition further comprises a surfactant.
  • the presence of one or more surfactants in the composition may be preferred in certain applications.
  • the inorganic halide mixture compromises a mixture of inorganic halides selected from metal halides and ammonium halides.
  • Typical metal halides include alkaline earth and alkali metals. Preferred are sodium and potassium alkali metals.
  • the inorganic halide mixture comprises two or more metal halides selected from the group consisting of potassium chloride, potassium bromide, potassium iodide, sodium bromide, sodium chloride and sodium iodide. Fluoride compounds may be toxic to plants and animals.
  • the inorganic halide mixture is a mixture of a chloride salt and a bromide salt.
  • the inorganic halide mixture is a potassium chloride and sodium bromide mixture.
  • the inorganic halide mixture is a sodium chloride and sodium bromide mixture.
  • a mixture of potassium chloride and potassium bromide or a mixture of sodium chloride and potassium bromide is provided.
  • the inorganic halide mixture excludes an iodide salt.
  • the inorganic halide mixture is provided at a range of from about 3% wt/wt to about 20% wt/wt. In some embodiments the inorganic halide mixture is provided at a range of from about 5% wt/wt to about 15% wt/wt. In other embodiments the inorganic halide mixture is provided at about 10% w/w.
  • the inorganic halides can be provided in various proportions. In some embodiments the ratio of bromide salt to chloride salt is about 3 :7 wt/wt to about 9: 1 wt/wt. In preferred embodiments the bromide salt to chloride salt are provided at about 1 : 1 ratio wt/wt. In preferred embodiments the inorganic halide mixture comprises about 5% wt/wt bromide salt and about 5% wt/wt chloride salt.
  • At least one oxidizing agent is preferably selected from an agent capable of reacting with an inorganic halide to generate hypohalite ions.
  • the at least one oxidizing agent is provided in an amount from about 25% wt/wt to about 60% wt/wt. In some embodiments at least one oxidizing agent is provided in an amount about 35% wt/wt to about 55% wt/wt. In specific embodiments at least one oxidizing agent is provided at about 50% w/w.
  • the oxidizing agent may be selected from the group consisting of a persulfate compound and a peroxyphthalate compound.
  • the oxidizing agent is a peroxyphthalate compound e.g., potassium monoperoxyphthalate. In certain preferred embodiments the oxidizing agent is a persulfate compound. In specific embodiments the persulfate compound is potassium hydrogen peroxymonosulfate sulfate.
  • Sulfamic acid is an provided in an amount of about 3% wt/wt to about 10% wt/wt. In some embodiments, sulfamic acid is provided at about 5% wt/wt to about 8% wt/wt. In a currently preferred embodiment sulfamic acid is provided at about 5% wt/wt.
  • At least one non-reducing organic acid is provided in the present composition in an amount of about 3% wt/wt to about 20% wt/wt. In some embodiments the non- reducing organic acid is provided in an amount about 5% wt/wt to about 15% wt/wt. In specific embodiments a non-reducing organic acid is provided in an amount of about 8% wt/wt to about 10% wt/wt.
  • the organic-based acid is selected from malic acid, tartaric acid, citric acid, acetic acid, glycolic, glutamic acid, sorbic acid, benzoic acid, or dimeric acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, etc., or fatty acids such as butyric acid, caprylic acid, caproic acid, octanoic acid, nonanoic acid, decanoic acid, and the like; or mixtures thereof.
  • the at least one non-reducing organic acid is selected from malic acid, adipic acid and succinic acid.
  • the non-reducing organic acid is malic acid.
  • At least one alkali metal phosphate is provided in the present composition in an amount of about 5% wt/wt to about 30% wt/wt. In some embodiments an alkali metal phosphate is provided at about 10% wt/wt to about 20% wt/wt. In a currently preferred embodiment an alkali metal phosphate is provided at about 10% wt/wt.
  • the anhydrous alkali metal phosphate can be any alkali metal phosphate known in the art.
  • the anhydrous alkali metal phosphate is selected from sodium hexametaphosphate, tetrasodium diphosphate, tetrasodium pyrophosphate, mono- sodium phosphate, di-sodium phosphate, tri-sodium phosphate, mono-potassium phosphate (MKP), di-potassium phosphate, tri-potassium phosphate and combinations thereof.
  • the alkali metal phosphate is MKP.
  • MKP is provided in an amount of about 10% wt/wt of the composition.
  • chemical filler is an inert inorganic hygroscopic salt selected from the group consisting of calcium carbonate, magnesium silicate, sodium silicate, sodium carbonate, calcium bicarbonate, potassium bicarbonate and combinations thereof.
  • the chemical filler is calcium carbonate.
  • a surfactant compatible with the acids and oxidizing agents is acceptable.
  • the surfactant may be selected from the group consisting of lauryl ether sulfates, ethylene oxide, propylene oxide aklyl phenol condensates, polyglycol ethers of fatty alcohols, fatty acid ethylene oxide condensates, polyglycol ethers of alkyl phenols, fatty alcohol ethoxylates and combinations thereof.
  • a preferred surfactant is sodium dodecylbenzene sulphonate.
  • the surfactant can be provided in the composition at a concentration of about 5% wt/wt to about 20% wt/wt. Preferably, the surfactant is provided in an amount of about 10% wt/wt.
  • the composition is preferably prepared as a solid in a form selected from the group consisting of powder, tablet, dispersion, granules, pill, capsule and microcapsules.
  • the compositions may be prepared as controlled-release or slow-release compositions.
  • the composition is provided as a powder that is soluble in an aqueous medium.
  • the powder is applied as is.
  • an aqueous solution is prepared immediately prior to use.
  • the composition is prepared as a semi-solid, for example as a paste or cream.
  • compositions are useful as a soil sanitizer.
  • the compositions are non- phytotoxic and therefore show utility in pre-planting soil sterilization and post-planting soil treatment.
  • composition of the present invention is diluted about 2- to about 7-fold with nonorganic, inert chemical filler. In certain preferred embodiments the composition is diluted about 4-fold.
  • the present invention further provides a non-phytotoxic biocidal composition for soil disinfestation comprising about 15% wt/wt to about 50% wt/wt of a composition comprising
  • At least one non-organic inert filler the pH of a 1% by weight aqueous solution of the composition being between 1.2 and 5.5; and about 50% wt/wt to about 85% wt/wt of a non-organic, inert chemical filler.
  • the non-organic chemical filler is selected from the group consisting of calcium carbonate and sodium carbonate (soda ash).
  • the method of applying the composition is not limiting.
  • the composition is nsedper se.
  • the composition is blended with non-organic inert chemical filler.
  • the present invention provides a method for soil disinfestation comprising the step of: a) applying to the soil a biocidal-effective amount a composition according to the present invention.
  • the method further comprises the step of: b) blending said composition into the soil.
  • compositions including powder
  • the composition is formulated as liquid and can be applied using suitable means, including by spray or drip irrigation.
  • compositions of the present invention are useful in seed and fish disinfection. Accordingly, the present invention provides a method for the disinfection of fish comprising the steps of: a) preparing a solution comprising a biocidally-effective amount of a composition comprising:
  • the solution may further comprise about 1% wt/v to about 5% wt/v pyrogen.
  • the solution is effective in eradicating parasites and microbes that infect fish.
  • a biocidally effective solution comprises about 0.05% wt/v to about 20% wt/v of the composition, preferably about 0.5% wt/v to about 2% wt/v of the composition in order to be an effective, yet harmless, disinfectant of the fish.
  • the composition is effective in treating fish tanks, aquariums and is useful in treating fishponds and fish farms.
  • the present invention also provides a method for the disinfection of seeds comprising the steps of: a) preparing a solution comprising a biocidally-effective amount of a composition comprising:
  • a biocidally effective solution comprises about 0.05% wt/v (weight per volume) to about 20% wt/v composition, in order to be effective in disinfection, yet harmless to the seeds.
  • a seed disinfecting solution comprises about 0.1% wt/v to about 5% wt/v of the composition of the present invention.
  • Sufficient time for disinfection is preferably less than 1 hour, and more preferably less than 30 minutes.
  • composition of the present invention is also useful in treating post-harvest produce and in disinfecting animal and their surroundings.
  • Figure 1 demonstrates the level of CFU (colony forming units) of microorganisms present in the soil following treatment of soil with the compositions of the present invention.
  • Figure 2 shows seedlings sprouted from seeds treated with composition 21 and composition 22.
  • Figure 3 demonstrates the level of disinfection offish as a reduction in CFU following treatment with composition 21.
  • the present invention is directed to novel antimicrobial/disinfestation compositions and utility thereof, particularly in agricultural applications.
  • the invention discloses for the first time a composition comprising a plurality of inorganic halides as a highly effective disinfectant.
  • the composition is an effective, non-phytotoxic antimicrobial agent suitable for soil disinfestation, seed disinfestation, and animal disinfection.
  • the composition is applicable as a soil sanitation composition both for use prior to planting and during the growing season.
  • the advantages of the present composition include the following: a) The compositions comprise a combination of at least two inorganic halides, which provide an unexpectedly effective biocidal activity; b) Non-phytotoxic composition that is highly effective for soil disinfestation before seeding or planting and for soil treatment during the growing season; c) Broad spectrum composition effective in eradication soil pests including plant root viral, nematode and bacterial diseases; d) Safe for use on and within vicinity of animals, including fish and livestock; e) The reactivation process results in reduction in the total amount of halogen needed for the sterilization process, thereby reducing the soil and water source contamination. f) The compositions are stable and active in soil and in the presence of organic matter; g) The compositions are stable and do not liberate halide gas in the dry state.
  • Halides are released upon exposure to water at a pH less than 3.
  • the compositions can be applied to the soil as a liquid composition or as a dry composition;
  • Composition comprising a low bromide concentration, compared to methyl bromide soil fumigation, thereby eliminating danger of ozone damage;
  • the danger associated with chlorine evolution is obviated while enhancing the biocidal activity through the use of a mixture of two or more halides.
  • the phosphates act as buffering and chelating agents, in combination with the pH stability of sulphamic acid, enable the compositions of the present invention to be effective over a wide range of conditions.
  • the composition can be dissolved in hard water or in seawater without deleteriously affecting its biocidal properties.
  • the invention provides a dry, water-soluble biocidal composition
  • a dry, water-soluble biocidal composition comprising (a) from about 3% to about 20% wt/wt of a water-soluble mixture of at least two inorganic halides;
  • the present invention provides a dry, water-soluble biocidal composition
  • a dry, water-soluble biocidal composition comprising: (a) from about 3% to about 20% wt/wt of a water-soluble mixture of at least two inorganic halides;
  • composition further comprises from about 1% to about
  • the present invention provides a dry, water-soluble biocidal composition comprising:
  • the present invention provides a dry, non- phytotoxic composition comprising: (a) from about 3% to about 20% wt/wt of a water-soluble mixture of at least two inorganic halides;
  • dry refers to a composition comprising less than 10% moisture, and preferably less than 5% moisture.
  • biocidal refers to the reduction in the number of one or more pathogen species in a treated sample compared to an untreated sample. In one embodiment a reduction of at least 10% in the number of at least one pathogen is biocidally effective. In preferred embodiments, a reduction of at least 50% is biocidally effective.
  • the inorganic halides comprise a mixture of two water- soluble inorganic halides. In certain embodiments the inorganic halides are provided in equal amounts wt/wt. In some embodiments the inorganic halide mixture compromises a mixture of inorganic halides selected from metal halides and ammonium halides. Typical metal halides include alkaline earth and alkali metals. Preferred are sodium and potassium alkali metals. In one preferred embodiment, the inorganic halide is a mixture of potassium chloride and sodium bromide. In certain embodiments the inorganic halide mixture is provided at a concentration of about 3% to about 20% w/w. In other embodiments the inorganic halide mixture is provided at a concentration of about 5% to about 15% w/w. In other embodiments the inorganic halide mixture is provided at about 10 % wt/wt.
  • the preferred inorganic halide mixture is potassium chloride and sodium bromide mixture
  • any other mixture of inorganic halides can be substituted, for example, mixtures of potassium chloride, potassium bromide, potassium iodide, sodium bromide, sodium chloride or sodium iodide, are acceptable provided that they do not react with the components of the composition to form an insoluble salt.
  • the inorganic halide mixture is a mixture of potassium chloride and potassium bromide.
  • the inorganic halide mixture is a mixture of sodium chloride and sodium bromide.
  • compositions comprising an inorganic halide mixture comprising a mixture of three or more inorganic halides.
  • the composition comprises, for example, a mixture of NaCl, KCl and KBr.
  • the amount of non-organic inert chemical filler is increased proportionately.
  • the filler acts as a buffer.
  • At least one oxidizing agent is provided in an amount about 35% to about 55% wt/wt. In specific embodiments the at least one oxidizing agent is provided at about 50% wt/wt.
  • the oxidizing agent is preferably selected from an agent capable of reacting with the inorganic halides to generate hypohalite ions.
  • the oxidizing agent can be selected from the group consisting of a persulfate compound and a peroxyphthalate compound.
  • the oxidizing agent is a peroxyphthalate compound and in particular embodiments is potassium monoperoxyphthalate.
  • the oxidizing agent is a persulfate compound.
  • the persulfate compound is the commercially available potassium hydrogen peroxymonosulfate (Oxone®), represented by the chemical formula 2KHSO 5 -KHSO 4 -K 2 SO 4 [CAS-RN 70693-62-8].
  • Sulfamic acid is provided in an amount of about 3% to about 10% wt/wt. In some embodiments, sulfamic acid is provided at about 5% to about 8% wt/wt. In some embodiments, sulfamic acid is provided at about 5% wt/wt.
  • At least one non-reducing organic acid is provided in the present composition in an amount of about 3% to about 20% wt/wt. In some embodiments the non-reducing organic acid is provided in an amount of about 5% to about 15% wt/wt. In certain embodiments the non-reducing organic acid is provided in an amount of about 5% to about 10% wt/wt. In specific embodiments a non-reducing organic acid is provided in an amount of about 8% wt/wt. In some embodiments the at least one non-reducing organic acid is selected from malic acid, adipic acid and succinic acid. In specific embodiments the non-reducing organic acid is malic acid.
  • At least one alkali metal phosphate is provided in the present composition in an amount of about 5% to about 30% wt/wt. In some embodiments an alkali metal phosphate is provided at about 10% to about 20% wt/wt.
  • the alkali metal phosphate can be any alkali metal phosphate known in the art.
  • the alkali metal phosphate is selected from sodium hexametaphosphate, tetrasodium pyrophosphate, mono- sodium phosphate, di-sodium phosphate, tri-sodium phosphate, mono-potassium phosphate (MKP), di-potassium phosphate, tri-potassium phosphate and mixtures thereof.
  • the composition comprises about 10% MKP as a preferred alkali metal phosphate.
  • the invention provides a dry, water-soluble biocidal composition comprising: (a) about 10% wt/wt mixture of potassium chloride and sodium bromide
  • the inorganic halide mixture comprises potassium chloride (KCl) and sodium bromide (NaBr).
  • KCl potassium chloride
  • NaBr sodium bromide
  • This composition was unexpectedly found to be substantially more effective than hitherto known compositions comprising a single halide.
  • the composition of the invention was unexpectedly found to be about 100 times more active as a soil-sanitizing agent than a composition comprising a single halide, specifically a composition comprising sodium chloride composition 22 or Virkon ® -S.
  • the inorganic halide mixture comprises sodium chloride
  • the inorganic halide mixture comprises potassium chloride (KCl) and potassium bromide (KBr).
  • composition of the present invention is able to reactivate the halides, resulting in reduced halide consumption.
  • biocidal advantages of bromides, and the specific synergistic effect of the bromide- chloride formulation can be utilized with minimized environmental damage.
  • the presence of one or more surfactants in the composition is optional and can be preferred in some applications, in particular for seed disinfection and veterinary applications.
  • a surfactant compatible with the acids and oxidizing agents is acceptable.
  • the surfactant can be selected from the group consisting of lauryl ether sulfates, ethylene oxide aklyl phenol condensates, propylene oxide aklyl phenol condensates, polyglycol ethers of fatty alcohols, fatty acid ethylene oxide condensates, polyglycol ethers of alkyl phenols, fatty alcohol ethoxylates and combinations thereof.
  • Preferred surfactants include sodium dodecylbenzene sulphonate and sodium lauryl benzene sulfate.
  • the surfactant can be provided in the composition at a concentration of about 5% wt/wt to about 20% wt/wt.. Preferably the surfactant is provided to about 10% wt/wt.
  • the present invention further provides utility and methods of using the disclosed compositions.
  • the compositions of the invention are useful in diverse applications due to their low toxicity to plants and animals.
  • the compositions of the present invention have been shown to be effective in soil disinfestation for the effective control of soil-borne plant pathogens, including soil-borne pests such as bacteria, nematodes, fungi, viruses, protozoa, mycoplasmas and insects.
  • soil-borne pests such as bacteria, nematodes, fungi, viruses, protozoa, mycoplasmas and insects.
  • the compositions are useful in the treatment of soil either before planting or during the growing season. Plant pathogens cause significant global agricultural devastation annually, including damage to and loss of crops and flowers in nurseries, greenhouses, fields and groves.
  • Bacterial pathogens have a significant impact. Bacterial pathogens include species of Pseudomonas; Erwinia; Agrobacteria; Xanthomonas; Clavibacter; Xylella and others. For example, Erwinia species cause blight, wilt, or soft-rot in numerous trees, flowers, produce and crops. Xanthomonas species cause spots, wilts, rots and cankers in a variety of citrus trees and vegetable plants.
  • Fungal plant pathogens include species from the genera Alternaria; Ascochyta; Botrytis; Cercospora; Colletotrichum; Diplodia; Erysiphe; Fusarium; Gaeumanomyces; Helminthosporium; Macrophomina; Nectria; Peronospora; Phoma; Phymatotrichum; Phytophthora; Plasmopara; Podosphaera; Puccinia; Pythium; Pyrenophora; Pyricularia; Rhizoctonia; Scerotium; Sclerotinia; Septoria; Thielaviopsis; Uncinula; Venturia; Verticillium and others.
  • Plant pathogenic nematodes include nematodes of the economically important Heterodera; Meloidogyne and Pratylenchus species among others causing diseases such as root galls, root rot, stunting and various other rots.
  • nematodes serve as vectors for viral plant pathogens.
  • Agriculturally important insects include those species that attack plants directly and those that are vectors of plant pathogenic microbes.
  • the method of applying the compositions is not limiting.
  • the compositions can be added to the soil in solid, semi-solid or liquid form.
  • a solid the composition can be added to the soil in an amount of about 100 kg to about 500 kg per 1,000 square meters (m 2 ) of a 1:4 diluted composition.
  • a liquid about 250 liter (1) to about 1000 1 of a 10% solution is adequate.
  • more or less material can be added to the soil.
  • a dilution of the solid composition is preferred for application to the soil.
  • the present invention further provides a solid composition for soil disinfestation comprising about 15% wt/wt to about 50% wt/wt of a composition comprising (a) from about 3% wt/wt to about 20% wt/wt of a water- soluble mixture of at least two inorganic halides; (b) from about 25% wt/wt to about 60% wt/wt of at least one oxidizing agent which, in aqueous solution, reacts with the halide to generate hypohalite ions; (c) from about 3% wt/wt to about 10% wt/wt sulphamic acid;
  • the method for soil disinfestation comprises the step of a) applying to the soil a biocidal-effective amount of the composition of the present invention. In additional embodiments the method for soil disinfestation further comprises the step of: b) blending said composition into the soil.
  • compositions of the present invention show utility in seed disinfection and in fish farm ponds and aquarium disinfection.
  • the present invention provides a method for seed disinfection comprising the steps of: a) preparing a dilute aqueous solution of the composition of the invention; and , b) wetting the seeds in said solution.
  • a typical seed treatment encompasses immersing seeds in a 0.05% to about 20% dilute solution of the composition.
  • the seeds are treated in a 0.1% to about 5% dilute solution for about 5 minutes to about 60 minutes.
  • the present invention provides a method for the disinfection offish comprising the steps of: a) preparing a dilute aqueous solution of the composition of the invention; b) exposing fish to said solution.
  • the composition is added to a vessel containing fish including an aquarium, bowl, pond, lake, pool, fish farm and the like.
  • Example 1 Preparation of a Composition
  • composition 21 A biocidal composition, referred to herein composition 21, was prepared by mixing together the following ingredients:
  • composition 22 a similar composition comprising a single halide, specifically 10% NaCl, was prepared and used for comparison to composition 21 in different applications.
  • the composition comprising a single halide is referred to herein composition 22.
  • the potassium persulphate triple salt (potassium hydrogen peroxymonosulfate) has the general formula 2KHSO 5 *KHSO 4 -K 2 SO 4 and is commercially available as Oxone®.
  • the mono potassium phosphate known as MKP, is provided as powder or granules.
  • Composition 21 was prepared by first preparing a potassium chloride/sodium bromide mixture by mixing together equal amounts by weight of the two salts. The potassium chloride/sodium bromide mixture was blended with the chemical filler, calcium carbonate. The compounds MKP, sulphamic acid, malic acid were added to the halide-filler mixture and finally, the resulting mixture was blended with the persulfate. A surfactant is optionally added. Composition 21 is stable and has a long shelflife.
  • a 1% by weight solution of the composition in de-ionized water had a pH of about 2.4.
  • the pH of the solution may vary, depending on the water source.
  • a dilute solid composition comprising a mixture of at least two inorganic halides, which is easily distributed and can be more uniformly dispersed through the soil. Therefore, the above composition was diluted (dry dilution) about 2-to about 7-fold in dry inert chemical filler, and tested for its biocidal activity in soil. A fourfold diluted composition is preferred.
  • Virkon ® -S is a commercially available (Antec, division of DuPont) biocide useful in cleaning and disinfection.
  • Virkon ® -S comprises a single halide (sodium chloride), potassium peroxomonosulfate, sulfamic acid, malic acid, sodium hexametaphosphate, and 15% surfactant.
  • Soil borne pathogens including bacteria, nematodes, fungi, viruses, insects and mycoplasmas provide a significant source of infection and economic damage to crops and ornamentals. Furthermore, the pathogens persist in the soil following plant removal and need to be eradicated prior to the subsequent planting season. Often, pathogens will infect plants and/or soil during the growth season and require prompt eradication.
  • Tests have been carried out to establish the biocidal activity of the above composition in accordance with the standard in soil pre-planting sanitation and disinfecting treatments of seeds.
  • Pathogenic fungi such as Fusarium species are both seed-borne and soil-borne. These pathogens affect many different hosts, including crops and ornamentals and result in immeasurable economic damage. Fusarium spp. is difficult to eradicate since compositions known to treat Fusarium are often toxic to the hosts.
  • the biocidal activity of the composition was tested by applying the present composition onto the soil surface and incorporating into the soil to various depths by tilling and or cultivation.
  • composition 21 was compared to composition 22 and to a commercially available composition, Virkon ® -S for efficacy in eradication of soil-borne pathogens.
  • Soil was infected with either a mixture of soil-borne pathogens including bacteria or Fusarium fungi. Columns were filled with infected soil. Compositions 21, 22 or Virkon ® -S were added to the column. The soil was watered and the soil was tested for pathogens at different depths.
  • Table 1 shows the number of colony forming units (CFU) of Fusarium remaining in the soil at a depth of 5 cm.
  • Control refers to untreated soil. All tests were performed in triplicate. All Pairwise Multiple Comparison Procedures (Fisher LSD Method) were used to compare the different treatments to each other. A statistically significant results were obtained for all tests comparing controls to composition 21.
  • CFU colony forming units
  • Table 1 Fusarium remaining in treated soil at a depth of 5 cm.
  • Table 2 Fusarium remaining in treated soil at a depth of 25 cm.
  • composition 21 eradicated all the fungi while composition 22- and Virkon ® -S-treated soil still has high numbers of fungi.
  • Table 3 Fusarium remaining in treated soil at a depth of 39 cm.
  • compositions of the present invention are useful soil disinfestation of bacteria. Soil-borne pathogens were added to the column and the number of bacteria (CFU) was counted. At a depth of 5 cm composition 21 was at least 10 times more effective and up to about 50 times more effective in eradicating bacteria (see table 4)
  • Table 4 Bacteria remaining in treated soil at a depth of 5 cm.
  • Table 5 Bacteria remaining in treated soil at a depth of 25 cm.
  • Table 6 Bacteria remaining in treated soil at a depth of 39 cm.
  • composition 21 performed significantly better that the commercially available mono-halide composition Virkon ® -S or composition 22.
  • Composition 21 was able to eradicate large numbers of pathogens in the soil, at various depths at about 10 to about 100 fold better than the monohalide compositions.
  • Example 4 Eradication of the bacteria, Erwinia carotavora, in Ivy plants
  • composition 21 was tested for effectiveness in treating Erwinia carotovora infection of Small leaf Ivy (Hedera helix). The composition was effective in eradicating the bacteria. Dilute aqueous solutions of 0.1%, 0.2%, and 0.3% of composition 21 were prepared. The product was applied to a 1 square meter quadrant at a rate of 1 liter of solution per meter by spray. The trial was repeated twice at each rate. No phytotoxicity signs have appeared after 48 hours the spread of the bacteria was arrested by the treatment.
  • Example 5 Disinfection of Cauliflower Seeds
  • composition 23 A composition further comprising a surfactant, sodium dodecylbenzene sulphonate, was added to the composition 21 to a final concentration of 10%. This composition is referred to herein as composition 23.
  • Cauliflowers seeds were infested with a mixture of soil-borne pathogens. The number of total bacterial, Xanthomonas, total fungi and Aspergillus was counted before and following treatment. Seeds were immersed in solutions of composition 23, diluted to a 0.1%, 0.5%, 1% or 2% aqueous solution in distilled water. Solutions of about 0.05% to about 20% w/v are acceptable. Table 7 shows the results of the experiment measured as CFU.
  • composition 23 eradicates most of the bacteria infecting the seeds, and all of the Xanthomonas species.
  • An aqueous solution of 0.5% of composition 23 eradicates more than 99% of the total fungi and all of the Fusarium species.
  • Figures 2A-C shows sprouting seeds following treatment with composition 23 compared to untreated seeds.
  • the petri dish on the left in Figure 2A shows untreated seeds that have begun to send out roots. Even at such an early stage, the start of fungal infection can be seen (marked by arrows), whereas the treated seeds in the petri dish on the right show no signs of fungal growth.
  • Figure 2B shows seedling grown from untreated seeds that have been stunted by the fungal growth (arrows).
  • Figure 2C shows that seedlings grown from seeds treated with composition 23 are disease free.
  • composition 24 a composition comprising a 10% mixture of KCl and NaBr and 10% surfactant (sodium dodecylbenzenesulphonate) in place of chemical filler, and optionally about about 1% to about 5% pyrogen.
  • An aqueous solution comprising about 0.05% to about 20% wt/v of composition 24 is acceptable.
  • Table 8 shows the reduction in the percent of infected fish over time following treatment with composition 21, composition 24 or malachite green (M. G.).
  • Livestock are sensitive to infection by a variety of parasites.
  • animals on dairy and poultry farms are highly susceptible to enteropathogens, which can cause a high degree of illness and even death, primarily among young animals.
  • enteropathogens can cause a high degree of illness and even death, primarily among young animals.
  • Cryptosporidiosis is a diarrheal disease caused by microscopic parasites of the genus Cryptosporidium. Once an animal or person is infected, the parasite lives in the intestine and passes in the stool. The parasite is protected by a chlorine resistant outer coating that allows it to survive outside the body for extended periods.
  • compositions of the invention were tested on calves and poultry. In a preliminary experiment, it was found that composition 23, at a final concentration of 5%, is efficient in destroying oocysts of Cryptosporidia under laboratory conditions. Furthermore, it was found that composition 23, at a final concentration of 4%, completely prevents the growth of Salmonella in a test tube. Prior to examining the effectiveness of this composition under field conditions, a safety test was conducted using a 5% aqueous solution of composition 23 on cattle and chickens.
  • the purpose of the experiment was to examine the safety of 5% composition of composition 23 on calves and chickens. Methods and materials; Two calves aged two months and 10 chickens, 6 weeks old, were used in the experiment. The bedding upon which the calves and chickens were housed was sprayed three times every two days with a preparation of 5% composition 23. After the final spraying, the animals were clinically examined daily over a period of two weeks. Results: The composition was harmless to the animals. No topical or systemic reaction to the composition was observed.
  • Example 8 Disinfection of cattle suffering from Cryptosp ⁇ ridiosis 1.
  • Cryptosporidiosis is very widespread in dairy farms and is caused by a single cell parasite Cryptosporidium parvum. The parasite multiplies in the small intestine and causes illness in calves aged 1-2 weeks. Signs of the disease include a lack of appetite, watery diarrhea and as a result of this, dehydration and sometimes even death, especially when the contagion is also accompanied with other enteropathogens (rota, corona, E. CoIi, salmonella). No effective medical preparations have been found to thwart the multiplication of these parasites in the intestine, which makes the disease very hard to prevent. Furthermore, the sterilization compositions are not sufficiently effective to prevent contagion.
  • composition 23 has been found to be effective in destroying the Cryptosporidia under laboratory conditions. Exposure of the parasite to concentrations of 1% and 5%, caused a precipitous drop in the number of oocysts already after a short exposure of half an hour (39% up to 53%), and with an exposure or 6 hours duration at these concentrations, a very significant reduction was observed of 71% up to 88%. From these results, composition 23 is effective in destroying the oocysts of Cryptosporidia in the test tube. A field experiment was conducted to its efficacy at a dairy farm suffering from a Cryptosporidia epidemic.The objective of this experiment was to examine the influence of composition of the present invention on Cryptosporidia infection among calves.
  • the calves were followed-up every day from age 5 to 16 days for the appearance of clinical signs of Cryptosporidiosis and for the presence and quantity of the oocysts in samples of feces taken from each calf separately. Twice during the duration of the experiment, fecal samples from several of the calves in the experiment were examined for the presence of other enteropathogens (bacterial and viral).
  • Fecal samples were analyzed using the Zihal-Nelson method.
  • five gram (5g) of feces were dissolved in 20 ml of water, mixed and filtered through a 100- mesh filter. After mixing the solution, 10 microliters ( ⁇ l) were transferred to a microscope slide. After drying, the plate underwent fixing with methanol for two minutes, stained with concentrated Carbol fuchsin for 30 minutes, removing the staining with a 10% solution OfH 2 SO 4 for about 10 seconds and an additional staining with a 0.5% solution of Brilliant green. With this method of staining, Cryptosporidia oocysts were identified under the microscope at a magnification of 400X.
  • the oocysts were seen colored red on a green background on the slide.
  • a calculation of the oocysts per gram of feces was made by multiplying the number of oocysts counted on the complete slide by 500 (the dilution factor).
  • the efficiency of the treatment was determined by comparing the quantity of oocysts excreted by the calves before and after spraying with a 5% solution of composition 23. Results and discussion: The excretion of Cryptosporidia oocysts in calves before and after spraying the bedding with a 5% solution of composition 23. Results for the presence of Cryptosporidia oocysts in feces are detailed in Table 9.
  • Example 9 Bromide residues from the present composition in soil water runoff and the atmosphere.
  • Tests were conducted at three different concentrations of the composition, at 750, 1,500 and 3,000 PPM. Three repeat experiments were conducted at all concentrations in order to obtain statistical reliability (a total of 36 tests including a control with 3 repetitions).
  • the test was conducted within a glove chamber/sealed air chamber into which were placed:
  • Composition 21 at a suitable concentration was blended with the top 10 cm of soil in the column (the lower 30cm of soil in the column was not treated by the composition).
  • the column was wetted with water (eluent), eluate collection was started and the air spin pump was operated for a period of 24 hours.
  • the eluate was collected and sent for bromine concentration testing.
  • the air pump within the sealed chamber was operated for 12 hours, at the end of which, the fixing solution was sent to evaluate the bromine concentration.
  • composition required for the treatment of the (internal surface) volume of the column is 15 g. 1.3 Additional concentrations of composition: 3 g and 4.5 g for the column.
  • composition 1.4 A quantity of the composition must be mixed with 1,000 cc of soil of the chamra-sand type.
  • composition 2.2 Volume of the column is 3.2 liters.
  • Soil Chamra-sand (garden fill sand) or heavy clay soil.
  • Fixing solution a solution of SMBS (sodium meta-bisulfate) at a concentration of 0.05%.
  • the column was sealed, and two liters of tap water were run into it using an electric feed pump. After adding the water, the spin taps were opened and the pump was operated for 20 hours. At the end of the spinning, the soil was extracted. All of the samples were sent to an independent laboratory for testing.
  • Sample 1 composition concentration equivalent to 200 kg active ingredient/1, 000 m 2 : 1.5g for the column:
  • composition 21 1 gram of active ingredient of composition 21 diluted (dry dilution; cut) 4 fold in calcium carbonate were prepared.
  • Sample 2 composition concentration of 400 kg active ingredient/ 1,000 m 2 : 3.0 grams for the column: 3g of the preparation was mixed with sand to the top 10cm of the column. Water was fed into the column and the experiment proceeded as above (control).
  • Sample 3 composition concentration of 800 kg active ingredient/1, 000 m 2 : 6.0 grams for the column:
  • volume of eluate from sandy soil - 1 liter; from clay soil - 0.25 liter. Volume of fixing solution in the gas trap -0.5 liter. Concentration of SMBS in the sample water - 0.05% Duration of air spin after application- 20 hours.
  • Method of soil extraction - 20Og of soil will be mixed with 0.5 liter of SMBS solution and sent for bromide assay.
  • Method of preparing the 0.05% SMBS solution 2.5g of sodium meta-bi-sulfite powder were added into 5 liter of distilled water and mixed for 10 minutes by an electric magnetic mixer. Quantities of composition 21 for experiment purposes were 1.5g, 3g and 6g, for a column with sand at a volume of 3 liters.
  • Bromides in the soil To tests for residues in the soil show that the level is so low that it is not possible to identify any residues .
  • Bromides in run-off water The level of bromides found in the eluate is proportional to the quantity of the composition fed into the column.
  • the quality of the composition used in the experiment was at a concentration of 100% active ingredient.
  • a composition whose concentration of active ingredient is 20% (diluted about 1 :5), so that the data obtained regarding the concentration of bromides in run-off water are higher by a factor of 5 of the quantities produced owing to the ordinary application of the material.
  • the level drops so that practically no bromide would reach the underground water reserves
  • Table 11 shows the bromide concentrations in run-off water, soil and air after sterilizing soil with a composition of the invention.
  • Table 11 Bromide concentrations

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

La présente invention concerne des compositions agricoles et vétérinaires biocides et non toxiques, en particulier des compositions efficaces pour la désinsectisation avant la plantation et après la plantation, ainsi qu'un traitement de graines, de plantes et un produit comprenant un mélange d'au moins deux halogénures inorganiques et, l'utilisation de ces compositions dans des applications agricoles.
PCT/IL2005/000917 2005-08-25 2005-08-25 Compositions biocides non phytotoxiques destinee a un usage agricole et veterinaire WO2007023481A1 (fr)

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PCT/IL2005/000917 WO2007023481A1 (fr) 2005-08-25 2005-08-25 Compositions biocides non phytotoxiques destinee a un usage agricole et veterinaire
IL189745A IL189745A0 (en) 2005-08-25 2008-02-25 Non-phytotoxic biocidal compositions for agricultural and veterinary use

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7811971B2 (en) * 2007-12-06 2010-10-12 United Chemical Corp. Combination algae killer and surface stain remover
US10400198B2 (en) 2016-08-25 2019-09-03 Eagle Us 2 Llc Method of sanitizing a surface
EP3574759A1 (fr) * 2018-06-01 2019-12-04 LANXESS Deutschland GmbH Composition désinfectante
CN112074188A (zh) * 2018-05-04 2020-12-11 埃科莱布美国股份有限公司 非氯化氧化性杀生物剂化学物质、其生产方法、应用及其进料方法
CN112450227A (zh) * 2020-12-02 2021-03-09 岳阳才益精细化工有限公司 一种过硫酸氢钾复合盐泡腾片的制备方法
WO2021161148A1 (fr) * 2020-02-10 2021-08-19 Virox Technologies Inc. Compositions antimicrobiennes contenant de l'acide peroxyphthalique et/ou un sel de celui-ci
CN113396931A (zh) * 2021-06-03 2021-09-17 上海蓝宇水处理股份有限公司 一种复合消毒剂及其制备方法
WO2023063003A1 (fr) * 2021-10-13 2023-04-20 オルガノ株式会社 Composition de désinfection et procédé de désinfection

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Publication number Priority date Publication date Assignee Title
US4822512A (en) * 1986-03-01 1989-04-18 Auchincloss Thomas R Biocidal, particularly virucidal, compositions

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US4822512A (en) * 1986-03-01 1989-04-18 Auchincloss Thomas R Biocidal, particularly virucidal, compositions

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7811971B2 (en) * 2007-12-06 2010-10-12 United Chemical Corp. Combination algae killer and surface stain remover
US10400198B2 (en) 2016-08-25 2019-09-03 Eagle Us 2 Llc Method of sanitizing a surface
CN112074188A (zh) * 2018-05-04 2020-12-11 埃科莱布美国股份有限公司 非氯化氧化性杀生物剂化学物质、其生产方法、应用及其进料方法
AU2019263480B2 (en) * 2018-05-04 2022-06-30 Ecolab Usa Inc. Non-chlorinated oxidizing biocide chemistries, their methods of production, application and methods of feed thereof
AU2019278586B2 (en) * 2018-06-01 2021-09-23 Lanxess Deutschland Gmbh Disinfectant composition
CN112203514A (zh) * 2018-06-01 2021-01-08 朗盛德国有限责任公司 消毒剂组合物
WO2019228980A1 (fr) 2018-06-01 2019-12-05 Lanxess Deutschland Gmbh Composition désinfectante
AU2019278586B9 (en) * 2018-06-01 2021-10-14 Lanxess Deutschland Gmbh Disinfectant composition
CN112203514B (zh) * 2018-06-01 2021-10-15 朗盛德国有限责任公司 消毒剂组合物
EP3574759A1 (fr) * 2018-06-01 2019-12-04 LANXESS Deutschland GmbH Composition désinfectante
US11427485B2 (en) 2018-06-01 2022-08-30 Lanxess Deutschland Gmbh Disinfectant composition
WO2021161148A1 (fr) * 2020-02-10 2021-08-19 Virox Technologies Inc. Compositions antimicrobiennes contenant de l'acide peroxyphthalique et/ou un sel de celui-ci
CN112450227A (zh) * 2020-12-02 2021-03-09 岳阳才益精细化工有限公司 一种过硫酸氢钾复合盐泡腾片的制备方法
CN113396931A (zh) * 2021-06-03 2021-09-17 上海蓝宇水处理股份有限公司 一种复合消毒剂及其制备方法
WO2023063003A1 (fr) * 2021-10-13 2023-04-20 オルガノ株式会社 Composition de désinfection et procédé de désinfection

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