WO2023220772A1 - Iodine solution - Google Patents

Iodine solution Download PDF

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Publication number
WO2023220772A1
WO2023220772A1 PCT/AU2023/050360 AU2023050360W WO2023220772A1 WO 2023220772 A1 WO2023220772 A1 WO 2023220772A1 AU 2023050360 W AU2023050360 W AU 2023050360W WO 2023220772 A1 WO2023220772 A1 WO 2023220772A1
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WIPO (PCT)
Prior art keywords
acid
iodine
composition
water
iodate
Prior art date
Application number
PCT/AU2023/050360
Other languages
French (fr)
Inventor
Nicky Thomas
Zlartko SUMICH
Original Assignee
Global Iodine Solutions Ltd
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Filing date
Publication date
Priority claimed from AU2022901343A external-priority patent/AU2022901343A0/en
Application filed by Global Iodine Solutions Ltd filed Critical Global Iodine Solutions Ltd
Publication of WO2023220772A1 publication Critical patent/WO2023220772A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00Other inorganic fertilisers
    • C05D9/02Other inorganic fertilisers containing trace elements
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/12Iodine, e.g. iodophors; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00Disinfectants; Antimicrobial compounds or mixtures thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P5/00Nematocides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/13Iodine; Hydrogen iodide
    • C01B7/14Iodine
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00Fertilisers containing potassium
    • C05D1/005Fertilisers containing potassium post-treatment

Definitions

  • the present invention relates to compositions comprising iodine salts for the formation of molecular iodine, and use of such compositions for agricultural and other uses.
  • Iodine is not generally considered an essential nutrient for land plants; however, iodine can be used in a number of roles for the improvement of crops.
  • Iodine solutions can be used to control microbial pathogens such as bacterial and fungal pathogens on plants and in the soil. It is also useful for the control of pests such as arthropods, nematodes, bacteria, fungi, oomycetes, algae, protozoa, viruses, and viroids.
  • microbial pathogens such as bacterial and fungal pathogens on plants and in the soil. It is also useful for the control of pests such as arthropods, nematodes, bacteria, fungi, oomycetes, algae, protozoa, viruses, and viroids.
  • Iodine occurs in various forms or species in aqueous or solutional environments.
  • Iodide (I ) molecular iodine (l 2 ), hypoiodous acid (HOI), iodate (IO3 ), triiodide (I3 ), and polyiodides (e.g., I 5 _ or l 7 ) are among these species, and each of them have varying physical and chemical characteristics.
  • iodine solutions The instability of many iodine solutions is caused primarily by the hydration of molecular iodine to form hypoiodous acid, which leads to the formation of iodate and the loss of iodine atoms from the complex solutional equilibrium, resulting in very low concentrations of molecular iodine.
  • the biocidal action of iodine solutions is primarily due to simple molecular iodine.
  • the present invention provides an iodine composition for agricultural administration of molecular iodine, the composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base.
  • the composition may be in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base.
  • the composition is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid and wherein an optional base is further provided in Part A or B.
  • composition is in the form of a two-part iodine composition, wherein:
  • Part A comprises: an iodate, an acid and an optional base; and ii.
  • Part B comprises: an iodide or i.
  • Part A comprises: an iodate; and ii.
  • Part B comprises: an iodide, an acid and an optional base or i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide and an optional base or i.
  • Part A comprises: an iodate and an optional base; and ii.
  • Part B comprises: an iodide and an acid.
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide and an optional base.
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide.
  • This composition may optionally further comprise a base as a Part C, to form a three part composition.
  • the acid is a strong acid, for example sulphuric acid.
  • a carboxylic acid such as citric acid may be used.
  • the base is a strong base, for example sodium hydroxide.
  • the iodate is potassium iodate, more preferably a potassium iodate powder or concentrate.
  • the iodide is potassium iodide, more preferably a potassium iodide powder or concentrate.
  • the Part A and Part B and optional Part C of the iodine composition are added to a volume of water for use.
  • the combination of the Part A and Part B and optional Part C of the iodine composition with the volume of water produces a dilute molecular iodine solution.
  • the pH of the dilute molecular iodine solution is below pH 6, for example below pH 5.5, or below pH 2.0 (preferably a pH of about 1 .6).
  • the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
  • the present invention also provides a method to control agricultural pathogens using an iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding optional Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the agricultural surface wherein i.
  • Part A comprises: an iodate and an acid;
  • Part B comprises: an iodide; and iii.
  • optional Part C comprises: a base wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0.
  • the pH may be below pH 2 (preferably a pH of about 1 .6) during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
  • the pathogens are soil, plant or animal agricultural pathogens.
  • the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the present invention further provides a method to control agricultural pathogens using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the agricultural surface wherein: i.
  • Part A comprises: an iodate, an acid and an optional base; and ii.
  • Part B comprises: an iodide or i.
  • Part A comprises: an iodate; and ii.
  • Part B comprises: an iodide, an acid and an optional base or i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide and an optional base or i.
  • Part A comprises: an iodate and an optional base; and ii.
  • Part B comprises: an iodide and an acid wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide and an optional base.
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide.
  • This composition may optionally further comprise a base as a Part C.
  • the present invention further provides a method to improve plant growth using a three- part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i.
  • Part A comprises: an iodate and an acid;
  • Part B comprises: an iodide; and iii.
  • Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, or below pH 2.8, preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the present invention further provides a method to improve plant growth using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i.
  • Part A comprises: an iodate an acid and an optional base; and ii.
  • Part B comprises: an iodide or i.
  • Part A comprises: an iodate; and ii.
  • Part B comprises: an iodide, an acid and an optional base or i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide and an optional base or i.
  • Part A comprises: an iodate and an optional base; and ii.
  • Part B comprises: an iodide and an acid wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide and an optional base.
  • the present invention further provides a method to increase the level of iodine in plant biomass using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i.
  • Part A comprises: an iodate and an acid;
  • Part B comprises: an iodide; and iii.
  • Part C comprises: a base wherein the amount of the acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the present invention also provides a method to increase the level of iodine in plant biomass using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii.
  • Part B comprises: an iodide, an acid and an optional base or i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide and an optional base or i.
  • Part A comprises: an iodate and an optional base; and ii.
  • Part B comprises: an iodide and an acid wherein the amount of the acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide and an optional base.
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide.
  • composition may optionally further comprise a base as a Part C.
  • the present invention further provides a kit for the formation of molecular iodine comprising: a) an iodine composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base; and b) instructions for use.
  • the kit for the formation of molecular iodine preferably comprises: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base b) instructions for use.
  • the kit for the formation of molecular iodine may alternatively comprise: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid b) instructions for use wherein an optional base is further provided in Part A or B.
  • the kit for the formation of molecular iodine preferably comprises: a) a two-part iodine composition, wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid. b) instructions for use.
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide.
  • this composition may optionally further comprise a base as a Part C.
  • the kit of the present invention comprising a three-part or two-part iodine composition is preferably added to a volume of water to form a dilute molecular iodine solution.
  • the amount of the acid and base in the iodine composition of the kit is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 after adding the iodine composition to the volume of water.
  • the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
  • Figure 1 is a graph of iodine conversion efficiency as a function of pH.
  • Figure 2 is a schematic of a first exemplary flow process for the manufacture of a dilute molecular iodine solution according to the present invention.
  • Figure 3 is a schematic of a second exemplary flow process for the manufacture of a dilute molecular iodine solution according to the present invention.
  • Molecular iodine is relatively unstable and readily sublimes, being rapidly lost to the atmosphere through diffusion.
  • Various methods such as complexed iodine (for example iodine attached to a high molecular weight moiety such as povidone (polyvinylpyrrolidone (PVP)) have been developed to produce stable, storable and transportable solution-based compositions of molecular iodine. I 2 cannot be concentrated, as the maximum solubility in water is about 330 ppm.
  • the inventors have developed an iodine composition, comprising a Part A, a Part B and an optional Part C, which when combined in solution forms molecular iodine.
  • the composition reduces the transport costs of iodine containing compositions for agricultural use.
  • the iodine solution can be diluted by mixing into a volume of water to form a dilute molecular iodine solution.
  • the pH of the solution will change, leading to changes in the concentration of l 2 .
  • the present invention provides a two- or three-part iodine solution.
  • the iodine solution comprises an acid and optionally a base to form a buffer, so that the pH is controlled during dilution.
  • the present invention provides an iodine composition for agricultural administration, the composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base.
  • the composition is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base.
  • the composition is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid and wherein an optional base is further provided in Part A or B.
  • the composition is in the form of a two-part iodine composition, wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid.
  • the composition comprises: i.
  • Part A comprises: an iodate and an acid; and
  • Part B comprises: an iodide.
  • composition may optionally further comprise a base as a Part C.
  • the acid is a food grade acid, so that the acid does not need to be removed from the agricultural surface (such as the crop surface, agricultural equipment, fruit or vegetable etc), before edible products come into contact with the surface or are consumed by humans or animals.
  • the acid is able to break down in the soil or water quickly so that the acid does not build up in the soil or water and change the pH over repeated application.
  • the acid is a strong acid.
  • the acid may be sulphuric acid, hydrochloric acid, nitric acid, chloric acid, hydrobromic acid, hydroiodic acid or perchloric acid. More preferably, the strong acid is sulphuric acid.
  • the acid may be a weak acid.
  • the acid may be formic acid, acetic acid, benzoic acid, oxalic acid, nitrous acid or sulfurous acid.
  • the weak acid may be a carboxylic acid.
  • a carboxylic acid is used, preferably the carboxylic acid is selected from the group consisting of formic acid, carbonic acid, carbon dioxide hydrate, acetic acid, glycolic acid, glyoxylic acid, oxalic acid, propionic acid, acrylic acid, propiolic acid, lactic acid, 3-hydroxipropionic acid, glyceric acid, pyruvic acid, malonic semialdehyde, mesoxalic semialdehyde, malonic acid, tartronic acid, dihydroxymalonic acid, mesoxalic acid, butyric acid, isobutyric acid, crotonic acid, isocrotonic acid, methacrylic acid, vinylacetic acid, tetrolic acid, 2-hydroxybutyric acid, 3- hydroxybutyric acid, 4-hydroxybutyric acid, a-ketobutyric acid, acetoacetic acid, succinic semialdehyde, succinic acid, methylmalonic acid, fumaric acid
  • the carboxylic acid is chosen from the list comprising: citric acid, malic acid, ascorbic acid, acetic acid, oxalic acid, tartaric acid, isocitric acid, citramalic acid, galacturonic acid, shikimic acid, lactic acid, quinic acid, succinic acid, and fumaric acids.
  • the carboxylic acid is selected from the group consisting of acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, tartaric acid and citric acid. Most preferably the carboxylic acid is citric acid.
  • the optional base is a food grade base, so that the base does not need to be removed from the agricultural surface (such as the crop surface, agricultural equipment, fruit or vegetable etc), before edible products come into contact with the surface or are consumed by humans or animals.
  • the base is able to break down in the soil or water quickly so that the base does not build up in the soil or water and change the pH over repeated application.
  • the base is a strong base.
  • the base is a hydroxide or carbonate.
  • the base may be sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, or calcium carbonate. More preferably the base is potassium hydroxide or potassium carbonate.
  • the combination of the acid and the base form a buffer system.
  • the formation of molecular iodine from the reaction between the iodate (IO3 ) and iodide (I ) that results in an equilibrium in solution between the triiodide ion (l 3 ) and free molecular iodine (I2) / iodide ion (I ) can cause an increase in pH of a solution as acid (H + ) is consumed via the formation of water (H 2 O).
  • the reaction of iodide and iodate in the presence of acid to produce molecular iodine may be expressed in accordance with the following equation:
  • the amount of l 2 that is generated is less than the stoichiometric value according to this equation.
  • the quantities of iodate and iodide may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% higher than the stoichiometric quantities predicted by the above equation.
  • the quantity of iodate is about 20% higher than the stoichiometric quantities predicted by the above equation (i.e. 120% of the predicted value).
  • the quantity of iodide is about 50% higher than the stoichiometric quantities predicted by the above equation (i.e. 150% of the predicted value).
  • the dilute molecular iodine solution according to the present invention is composed with 5% to 20% more iodide than iodate, more preferably 10% to 15% more iodide than iodate.
  • a base such as sodium hydroxide
  • a base such as sodium hydroxide
  • the pH of the volume of water and/or the dilute molecular iodine solution is buffered against a rise in pH, and preferably maintains the pH below pH 7.0, more preferably below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the pH may be below pH 2 during production of the dilute molecular iodine solution, the adjusted to a pH of 4 to 6 ready for use.
  • the pH of the dilute molecular iodine solution is preferably below pH 7.0, 7.5, 6.0, 5.5, 5.0, 4.5, 4.0, 3.5, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.5, 2.4, 2.3, 2.2, 2.1 , 2.0, 1 .9, 1 .8, 1 .7, 1 .6, 1 .5, 1 .4, 1 .3, 1.2, 1.1 , 1.0, 0.9, 0.8, 0.7, 0.6, or 0.5. More preferably the pH is between pH 2.8 and 1.0, more preferably between pH 2.0 and 1 .5, for example pH 1 .6 during production of the dilute molecular iodine solution.
  • pH of the molecular iodine solution may increase due to dilution.
  • the pH may be adjusted to a pH of 4 to 6 ready for use.
  • Such a pH is less likely to, for example, burn the leaves or tissues of plants to which it applied or change the pH of soil such that the soil microbiota is adversely affected.
  • a base assists to maintain anions in solution, created when protons (H + ) derived from the acid are consumed in the Dushman reaction.
  • protons (H + ) derived from the acid are consumed in the Dushman reaction.
  • anions catalyse the formation of molecular iodine and/or assist to push the solutional equilibrium between triiodide and iodine towards the formation of molecular iodine. Therefore, it is believed that the presence of a base serves the dual purpose of buffering against detrimental rises in pH, and catalysing the formation of molecular iodine in preference to triiodide.
  • the presence of a base also assists to increase the pH of the dilute molecular iodine solution if the agricultural surface to which the solution is to be applied would be damaged by a very acidic solution.
  • a very acidic solution for example, application of a very acidic solution to a plant’s leaves may damage the leaves.
  • the pH may be raised (for example above pH 2.0) to avoid acidic burning of the surface.
  • the pH may be adjusted to a pH of 4 to 6 ready for use.
  • the iodate is potassium iodate, sodium iodate, magnesium iodate, or calcium iodate. More preferably the iodate is potassium iodate.
  • the iodide is potassium iodide, sodium iodide, magnesium iodide, or calcium iodide. More preferably the iodide is potassium iodide.
  • the iodate is potassium iodate.
  • the iodide is potassium iodide.
  • the acid is sulphuric acid.
  • the base is potassium hydroxide or potassium carbonate. Most preferably the base is potassium hydroxide, the iodate is potassium iodate, the acid is sulphuric acid and the iodide is potassium iodide.
  • the or each of the parts of the iodine composition of the present invention may further comprise a polar solvent to form a solution or liquid.
  • the iodine composition may comprise:
  • Part C is formed of the base, the Part C is in solid form.
  • Part A and/or Part B and/or Part C of the iodine composition of the present invention are in the form of a solution comprising a polar solvent
  • the solution may be a solution in any polar solvent capable of dissolving in sufficient quantities the acid, base and iodate (Part A) or the iodide (Part B) components of the respective Parts, including, but not limited to dimethylsulfoxide (DMSO), dimethylformamide (DMF), lower alkyl alcohols (such as methanol, ethanol, propanol, butanol, ethylene glycol, propanediol, glycerol, etc), acetone, ammonia, dimethyl ether, diethyl ether, tetrahydrofuran, hydroxylamine, acetonitrile, and water, including mixtures of any of the aforementioned polar solvents.
  • DMSO dimethylsulfoxide
  • DMF dimethylformamide
  • lower alkyl alcohols such as methanol,
  • Part A and/or Part B and/or Part C of the iodine composition of the present invention are in the form of a solution
  • the solution is a solution in water.
  • Part A of the iodine composition contains an iodate.
  • Iodine in its iodate salt form is extremely stable at temperatures below 200°C without a reducing agent and will not decompose until the temperature reaches 500°C.
  • Part B of the iodine composition contains an iodide. Iodine in its iodide salt form is very stable.
  • the Part A and Part B and optional Part C of the iodine composition are added to a volume of water for use.
  • the combination of the Part A and Part B and optional Part C of the iodine composition with the volume of water produces a dilute molecular iodine solution.
  • the Part A and Part B and optional Part C may be added to a volume of water immediately before spraying or otherwise applying the resulting solution to the soil, crop, orchard etc.
  • the molecular iodine is present in the dilute molecular iodine solution at from 3 ppm to 330 ppm.
  • the molecular iodine may be present in the dilute molecular iodine solution at 3, 5, 10, 15, 20, 25, 30, 35, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320 or 330 ppm.
  • the molecular iodine is present in the dilute molecular iodine solution at about 30 ppm (preferably from a 300 ppm preconcentrated solution).
  • the preferable amount of molecular iodine present in the dilute molecular iodine solution will depend on the application of the solution.
  • the dilute molecular iodine solution can be used in a range of agricultural applications, by administration to agricultural surfaces.
  • administration to agricultural surfaces includes injection of the dilute molecular iodine solution into plants or trees.
  • the agricultural surfaces include both man-made surfaces such as machinery, storage facilities and equipment, and food storage and preparation equipment, but also natural surfaces such as plants and soils.
  • the amount of molecular iodine present in the dilute molecular iodine solution is from 150 ppm to 330 ppm.
  • the amount of molecular iodine present in the dilute molecular iodine solution is from 30 ppm to 100 ppm.
  • the dilute molecular iodine solution may also be used as a fungicidal treatment by injection into plants and trees at from 30 ppm to 100 ppm molecular iodine.
  • the amount of molecular iodine present in the dilute molecular iodine solution is from 3 ppm to 25 ppm.
  • the amount of acid in the iodine composition is sufficient to maintain the pH of the dilute molecular iodine solution at below pH 5.5, more preferably below pH 2.0.
  • the amount of acid in the iodine composition is preferably sufficient to maintain the pH of the dilute molecular iodine solution at below pH 1 , 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4 or 5.5.
  • the pH is between pH 2.8 and 1 .0, more preferably between pH 2.0 and 1 .5, for example pH 1 .6.
  • the pH may be below pH 2 during production of the dilute molecular iodine solution, the adjusted to a pH of 4 to 6 ready for use.
  • the amount of base in the iodine composition is sufficient to maintain the pH of the dilute molecular iodine solution at below pH 5.5, more preferably below pH 2.0.
  • the amount of base in the iodine composition is preferably sufficient to maintain the pH of the dilute molecular iodine solution at below pH 1 , 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4 or 5.5.
  • the pH is between pH 2.8 and 1 .0, more preferably between pH 2.0 and 1.5, for example pH 1.6.
  • the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
  • the feature of maintenance of the pH of the dilute molecular iodine solution after mixing the iodine composition comprising a Part A and a Part B and optional Part C with a volume of water is important to ensure that the molecular iodine remains in solution.
  • the iodine composition will be mixed by the user (farmer, orchardist etc) with the water that is available.
  • the total dissolved solids (TDS) of water used in agriculture is less than 1000 ppm, as higher salt concentrations are not suitable for growing. However, depending on the available water, the types of salts and/or the type of crop being grown, the TDS may be higher than 1000 ppm.
  • the present iodine composition is designed to be used with water in the pH range from 5.7 to 8.3.
  • the presence of an acid and a base in the iodine composition of the present invention is designed to provide a buffer in such conditions. For example, if the user is combining the iodine composition with water at pH 8.3, the pH can be maintained at 2.0 or lower by the presence of the acid and the base. If the user is combining the iodine composition with water at pH 5.7, the pH can be maintained at 2.0 or lower by the presence of the and the base. If the pH of the available water for dilution is outside the range of 5.7 to 8.3, the pH of the water may be first adjusted to within the range by adding a separate acid or base to the water before adding the iodine composition of the present invention.
  • the water at the site of mixing and application is “hard” water, i.e., water with large amounts of dissolved minerals, particularly calcium and magnesium.
  • Water hardness is the measurement of the amount of divalent cations dissolved in the tested water and is, therefore, related to total dissolved solids. The more divalent cations (calcium and magnesium carbonates, bicarbonates and sulfates) dissolved in the water the "harder” the water.
  • Such hard water is often alkaline. This may interfere with the ability of the acid and/or base to buffer the dilute molecular iodine solution to a suitable pH, as the acid will interact with the dissolved minerals and be neutralised.
  • the iodine composition sufficient acid and base must be present in the iodine composition to react with any alkaline hardness in the water and still maintain the dilute molecular iodine solution at a pH of from pH 2 to 6 (more preferably lower than pH 5.5, lower than pH 2.0, for example a pH of about 1 .6).
  • the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
  • the pH of the dilute molecular iodine solution is below pH 5.5, below pH 5 or below pH 4.5. More preferably the amount of acid and base in the iodine composition is sufficient to maintain the pH of the dilute molecular iodine solution at below pH 2.0 (for example a pH of about 1 .6).
  • the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
  • the iodide consumes all of the iodate in the reaction to generate molecular iodine, to reduce the amount of free unreacted iodate that could form triiodide.
  • the ratio of iodide to iodate in the dilute molecular iodine solution is from 10:0.5 to 5:1 (molar). Most preferably the ratio of iodide to iodate in the dilute molecular iodine solution is 5:1.2 (molar).
  • the ratio of iodide to iodate in the dilute molecular iodine solution is from 5:0.5 to 4:1 (weight). Most preferably the ratio of iodide to iodate in the dilute molecular iodine solution is 3.88:1.2 (weight).
  • the dilute molecular iodine solution according to the present invention is composed with 5% to 20% more iodide than iodate, more preferably 10% to 15 more iodide than iodate.
  • the Parts of the iodine compositions may be in the form of dry powders, or may be liquids.
  • the iodine is a two-part composition, with Part A in the form of a liquid comprising iodate and an acid, and Part be in the form of a liquid comprising iodide.
  • Part A of the iodine composition may be in the form of a dry powder comprising an iodate and an acid
  • Part B may be in the form of a liquid comprising an iodide
  • Part C may be in the form of a dry powder comprising a base.
  • molecular iodine added to agricultural surfaces, including plants and soil, has a number of benefits.
  • the presence of molecular iodine may:
  • the iodine composition of the present invention may be diluted with water or other solvents before application; preferably the iodine composition is dissolved or diluted in water to form a dilute molecular iodine solution before application to agricultural surfaces, including plants and soil.
  • the dilute molecular iodine solutions may be used on agricultural surfaces in roles such as:
  • disinfecting solutions for example disinfection of animal sheds, building, etc.; agricultural product handling equipment and premises; abattoirs and other food processing premises; freezer and cool rooms for agricultural products; nursery plant equipment, racking, seedling trays, etc.;
  • the present invention therefore provides a method to control agricultural pathogens using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i.
  • Part A comprises: an iodate and an acid;
  • Part B comprises: an iodide; and iii.
  • Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the pathogens are soil, plant or animal agricultural pathogens.
  • the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of the acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
  • the present invention also provides a method to control agricultural pathogens using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the agricultural surface wherein: i.
  • Part A comprises: an iodate, an acid and an optional base; and ii.
  • Part B comprises: an iodide or i.
  • Part A comprises: an iodate; and ii.
  • Part B comprises: an iodide, an acid and an optional base or i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide and an optional base or i.
  • Part A comprises: an iodate and an optional base; and ii.
  • Part B comprises: an iodide and an acid wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the volume of water to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
  • the dilute molecular iodine solution is administered at a rate of 500 L/ha to 5,000 L/ha of land area to which it is applied.
  • application rates when used as a soil steriliser/fumigant would be from 500 and 5000 L/ha.
  • Application rates when used as a fungicide/biocide would vary between 500 and 2,500 L/ha.
  • Application rates when used as a soil drench would be based on type of irrigation and amount of the formulation required to saturate root zone of the plant, but preferably less than 5,000 L/ha.
  • the molecular iodine is present at a concentration of from 150 ppm to 320 ppm in at least the top layer of soil after application of the dilute molecular iodine solution.
  • the concentration is at least 300 ppm in at least the top layer of soil after application.
  • the concentration is from 30 ppm to 150 ppm in at least the top layer of soil after application.
  • the concentration is from 30 ppm to 150 ppm in at least the top layer of soil after application.
  • examples of agricultural pathogens include: fungi (including Fusarium sp., Rhizoctonia sp., Sclerotinia sclerotium, Botrytis spp., Colletotrichum spp.), oomycetes (including Pythium sp., Phytophthora cinnamomi), bacteria (including mollicutes, Zymomonas sp., Erwinia sp., Agrobacterium sp., Xanthomonas campestris, Pseudomonas syringae), algae (including parasitic green algae), protozoa, nematodes, arthropods (including
  • the present invention further provides a method to improve plant growth using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i.
  • Part A comprises: an iodate and an acid;
  • Part B comprises: an iodide; and iii.
  • Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
  • the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
  • the present invention further provides a method to improve plant growth using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i.
  • Part A comprises: an iodate, an acid and an optional base; and ii.
  • Part B comprises: an iodide or i.
  • Part A comprises: an iodate; and ii.
  • Part B comprises: an iodide, an acid and an optional base or i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide and an optional base or i.
  • Part A comprises: an iodate and an optional base; and ii.
  • Part B comprises: an iodide and an acid wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
  • the improvement in plant growth is a result of increasing biomass and/or increasing the levels of antioxidants in the plants, and/or reducing, limiting or eliminating the deleterious effects of soil and/or plant pathogens and/or pests.
  • the present invention further provides a method to increase the level of iodine in plant biomass using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i.
  • Part A comprises: an iodate and an acid
  • Part B comprises: an iodide; and iii.
  • Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
  • the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
  • the present invention also provides a method to increase the level of iodine in plant biomass using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii.
  • Part B comprises: an iodide, an acid and an optional base or i.
  • Part A comprises: an iodate and an acid; and ii.
  • Part B comprises: an iodide and an optional base or i.
  • Part A comprises: an iodate and an optional base; and ii.
  • Part B comprises: an iodide and an acid wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
  • Application to plants and/or soil may be in the form of a spray applied using a pump-pack, hand spray or boom spray; applied using a hose or jet or crop-duster equipped aircraft; and through watering systems, i.e., trickle, mini sprinklers, flood irrigation, etc.
  • the solution may further be injected into plants or trees,
  • the results plant on growing may be biofortified with a greater amount of iodine in its tissues than one grown in the absence of the dilute molecular iodine solution of the present invention.
  • the dilute molecular iodine solution may be administered to an agricultural surface such as soil, plants, seeds, trees etc. for control of agricultural pathogens, improvement in plant growth, an increase in the level of iodine in plant biomass and/or a reduction in methane production in ruminant livestock.
  • the iodine composition of the present invention and/or dilute molecular iodine solution of the present invention may further comprise one or more of the following auxiliary components: inert carrier(s), surface active agent(s) such as a sticker or spreader, stabilizer(s) and/or dye(s).
  • the iodine composition may also be suspended in a carrier fluid, such as air, nitrogen, carbon dioxide or fumigant gas.
  • the iodine composition and/or dilute molecular iodine solution may comprise auxiliaries such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, frost protectants, biocides, thickeners and/or other auxiliaries, such as adjuvants, for example.
  • An adjuvant in this context is a component which enhances the biological effect of the iodine composition and/or dilute molecular iodine solution, without the component itself having a biological effect.
  • adjuvants are agents which promote the retention, spreading, attachment to the leaf surface, or penetration of the iodine composition and/or dilute molecular iodine into the soil.
  • compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants).
  • Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic or pseudoplastic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), colour (dyes/pigment dispersions), wash-off (film formers or sticking agents), evaporation (evaporation retardants), and other formulation attributes.
  • Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • the present invention provides a kit for the formation of molecular iodine comprising: a) an iodine composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base; and b) instructions for use.
  • the kit for the formation of molecular iodine preferably comprises: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base b) instructions for use.
  • the kit for the formation of molecular iodine may alternatively comprise: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid b) instructions for use wherein an optional base is provided in Part A or B.
  • the kit for the formation of molecular iodine may alternatively comprise: a) a two-part iodine composition, wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid b) instructions for use.
  • the kit When used, the kit preferably results in a composition for agricultural administration of molecular iodine.
  • the composition of the kit may be used for control of agricultural pathogens, improvement in plant growth, an increase in the level of iodine in plant biomass and/or a reduction in methane production in ruminant livestock.
  • the kit of the present invention comprising a three-part or two-part iodine composition is preferably added to a volume of water to form a dilute molecular iodine solution.
  • the amount of acid and base in the iodine composition of the kit is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 after adding the iodine composition to the volume of water.
  • the invention described herein may include one or more range of values (e.g. size, displacement and field strength etc).
  • a range of values will be understood to include all values within the range, including the values defining the range, and values adjacent to the range which lead to the same or substantially the same outcome as the values immediately adjacent to that value which defines the boundary to the range. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. Hence “about 80 %” means “about 80 %” and also “80 %”. At the very least, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
  • active agent may mean one active agent, or may encompass two or more active agents.
  • Total I It is generally accepted that the ICP/MS system with an alkaline digest of soil and liquid samples is the best for the measurement of total iodine.
  • Sodium Thiosulphate Titration A common, simple form of measuring molecular iodine is by sodium thiosulphate titration. The principle used is that, as iodine reacts with sodium thiosulphate (the oxidant) it is reduced to form iodide, and that iodine reacts with starch to form a dense blue colour. By reacting iodine in the presence of starch with a known volume and concentration of thiosulfate, an end point is reached when the blue suddenly disappears. This technique measures both l 2 and l 3 ’.
  • Photometric Measurement A portable photometric for measuring molecular iodine in the range 0 to 12.5 ppm.
  • Iodine Test Paper/Strips These comprise a colour reaction for the presence of molecular iodine in increments of from 5 to 50 ppm.
  • Iodine Gas Detector These measure molecular iodine in ranges of 0 to 2 ppm and 0 to 20 ppm.
  • ISOL 300 dilute iodine solution is made using ISOL300/A, ISOL300/B, ISOL300/C and water.
  • the dilute molecular iodine solution has a pH of approx. 4.5 and an iodate (IO3 ) to iodide (I ) ratio of 5:1 .2 (molar) or 3.88:1 .2 (weight).
  • ISOL300/B x100 concentrated solution comprising 4.907 kgs potassium iodide and 50 kgs citric acid mixed with water to make up 100 litres
  • ISOL300/C anhydrous sodium hydroxide granules
  • ISOL 100 dilute iodine solution is made using ISOL100/A, ISOL100/B, ISOL100/C and water.
  • the dilute molecular iodine solution has a pH of approx. 4.5 and an iodate (IO3 ) to iodide (I ) ratio of 5:1 .2 (molar) or 3.88:1 .2 (weight).
  • ISOL100/B x100 concentrated solution comprising 1.636 kgs potassium iodide and 40 kgs citric acid mixed with water to make up 100 litres
  • ISOL100/C anhydrous sodium hydroxide granules
  • Mixing 1000 litres: Start with 997.2 L of water in a mixing tank and remove two 5 L amounts. Water in main tank should be continually circulated. To one of the 5 L lots of water add the iodate or ISOL100/A and mix until fully dissolved, add this to the main tank. Then add the ISOL100/B. To the other 5 L lot of water, add the ISOL100/C and mix until fully dissolved, add to main tank. The solution is ready to use after 10 to 15 mins.
  • ISOL 25 dilute iodine solution is made using ISOL25/A, ISOL25/B, ISOL25/C and water.
  • the dilute molecular iodine solution has a pH of approx. 4.5 and an iodate (IO3 ) to iodide (I ) ratio of 5:1 .2 (molar) or 3.88:1 .2 (weight).
  • ISOL25/B x100 concentrated solution comprising 409g potassium iodide and 40 kgs citric acid mixed with water to make up 100 litres
  • ISOL25/C anhydrous sodium hydroxide granules
  • ISOL A potassium iodate 8.5 g dissolved in 1 .2 L of 20% (w/w) sulfuric acid and
  • ISOL A potassium iodate 8.5 g dissolved in 1 .2 L of 20% (w/w) sulfuric acid and
  • the ISOL A and ISOLB are added to a small volume of water (about 10 L or 10% of final volume) to generate molecular iodine at about 300 ppm and about pH 1 .6 (or at least below pH 2). After 10 minutes, the small volume of water is topped up to a final volume of 1000 L (10- fold dilution) to produce a 30 ppm dilute molecular iodine solution at about pH 2.5.
  • the pH of the dilute molecular iodine solution may be adjusted to about pH >4 (pH 4 to 6) with a base.
  • the base for example a hydroxide or carbonate of sodium or potassium
  • the base is provided in solid form to reduce further dilution of the dilute molecular iodine solution.

Abstract

An iodine composition for agricultural administration of molecular iodine, the composition comprising: v. an iodate; vi. an iodide; vii. an acid; and optionally viii. a base.

Description

Iodine Solution
TECHNICAL FIELD
[0001] The present invention relates to compositions comprising iodine salts for the formation of molecular iodine, and use of such compositions for agricultural and other uses.
BACKGROUND ART
[0002] Iodine is not generally considered an essential nutrient for land plants; however, iodine can be used in a number of roles for the improvement of crops.
[0003] Iodine solutions can be used to control microbial pathogens such as bacterial and fungal pathogens on plants and in the soil. It is also useful for the control of pests such as arthropods, nematodes, bacteria, fungi, oomycetes, algae, protozoa, viruses, and viroids.
[0004] The natural iodine content in soil is low and fertilizing with iodine derivatives has been shown to aid in biomass production and increase the antioxidant levels in plants, which in turn provides drought and stress resistance. It is hypothesized that when small doses of iodine are provided to crops in the presence of nitrogen-rich fertilizers, it enables the plants to assimilate nitrogen more rapidly and increases growth.
[0005] The presence of additional iodine in soil may also lead to increased levels of iodine in the resulting plant biomass and thus biofortification of any resulting food product or livestock feed. This type of crop treatment increases the amount of iodine in animal and human diets, ultimately combating iodine deficiency disorder. Furthermore, it has been found that the presence of increased iodine in ruminant diet can decrease the methane production of the animal, so by increasing the amount of iodine in the fodder provided to the animal, environmental benefits can be obtained in terms of reducing greenhouse gas production arising from livestock agriculture.
[0006] In medical literature, the word "iodine" is frequently used with imprecision to refer to a variety of chemical entities and complex formulations including various iodine species. Part of the reason for the inaccurate representation of iodine compositions in the art is due to imprecise analytical characterization methods. Throughout this specification, when referring to the l2 species in an aqueous or solutional environment, the term "molecular iodine" (l2) will be used. Commonly, measurement of l2 is performed via thiosulfate titration. However, this method also detects triiodide and hypoiodous acid along with molecular iodine (l2).
[0007] Iodine occurs in various forms or species in aqueous or solutional environments. Iodide (I ), molecular iodine (l2), hypoiodous acid (HOI), iodate (IO3 ), triiodide (I3 ), and polyiodides (e.g., I5 _ or l7 ) are among these species, and each of them have varying physical and chemical characteristics. The instability of many iodine solutions is caused primarily by the hydration of molecular iodine to form hypoiodous acid, which leads to the formation of iodate and the loss of iodine atoms from the complex solutional equilibrium, resulting in very low concentrations of molecular iodine. The biocidal action of iodine solutions is primarily due to simple molecular iodine.
[0008] There is a need for new, preferably stable and transportable, solutions of molecular iodine for compositions for agricultural and other uses; or at least the provision of alternative solutions of molecular iodine to compliment the previously known methods to prepare, deliver and apply iodine. The present invention seeks to provide an improved or alternative method for the preparation and application of solutions of molecular iodine.
[0009] The previous discussion of the background art is intended to facilitate an understanding of the present invention only. The discussion is not an acknowledgement or admission that any of the material referred to is or was part of the common general knowledge as at the priority date of the application.
SUMMARY OF INVENTION
[0010] The present invention provides an iodine composition for agricultural administration of molecular iodine, the composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base.
[001 1] The composition may be in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base.
[0012] Alternatively, the composition is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid and wherein an optional base is further provided in Part A or B.
[0013] Alternatively, the composition is in the form of a two-part iodine composition, wherein:
I. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid.
[0014] Preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base.
[0015] More preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide.
[0016] This composition may optionally further comprise a base as a Part C, to form a three part composition.
[0017] Preferably the acid is a strong acid, for example sulphuric acid. However, a carboxylic acid such as citric acid may be used. Preferably the base is a strong base, for example sodium hydroxide. Preferably the iodate is potassium iodate, more preferably a potassium iodate powder or concentrate. Preferably the iodide is potassium iodide, more preferably a potassium iodide powder or concentrate.
[0018] Preferably, after being transported to or near to the site where application of molecular iodine is required and prior to application to soil, plant material (crops, vegetables, fruit, seeds, cuttings, runners, tubers etc), water, agricultural equipment (animal and food processing equipment, animal sheds, cool storage rooms, nursery equipment etc), or other surfaces, the Part A and Part B and optional Part C of the iodine composition are added to a volume of water for use. The combination of the Part A and Part B and optional Part C of the iodine composition with the volume of water produces a dilute molecular iodine solution. Preferably the pH of the dilute molecular iodine solution is below pH 6, for example below pH 5.5, or below pH 2.0 (preferably a pH of about 1 .6). For example the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
[0019] The present invention also provides a method to control agricultural pathogens using an iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding optional Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the agricultural surface wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. optional Part C comprises: a base wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0. For example the pH may be below pH 2 (preferably a pH of about 1 .6) during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use. Preferably the pathogens are soil, plant or animal agricultural pathogens.
[0020] Alternatively, the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6). [0021] The present invention further provides a method to control agricultural pathogens using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the agricultural surface wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
[0022] Preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base.
[0023] More preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide. [0024] This composition may optionally further comprise a base as a Part C.
[0025] The present invention further provides a method to improve plant growth using a three- part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, or below pH 2.8, preferably below pH 2.0 (preferably a pH of about 1 .6).
[0026] Alternatively, the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
[0027] The present invention further provides a method to improve plant growth using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i. Part A comprises: an iodate an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
[0028] Preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base.
[0029] The present invention further provides a method to increase the level of iodine in plant biomass using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of the acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
[0030] Alternatively, the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
[0031] The present invention also provides a method to increase the level of iodine in plant biomass using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid wherein the amount of the acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
[0032] Preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base.
[0033] More preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide.
[0034] This composition may optionally further comprise a base as a Part C.
[0035] The present invention further provides a kit for the formation of molecular iodine comprising: a) an iodine composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base; and b) instructions for use.
[0036] The kit for the formation of molecular iodine preferably comprises: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base b) instructions for use. [0037] The kit for the formation of molecular iodine may alternatively comprise: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid b) instructions for use wherein an optional base is further provided in Part A or B.
[0038] The kit for the formation of molecular iodine preferably comprises: a) a two-part iodine composition, wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid. b) instructions for use.
[0039] More preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide.
[0040] This composition may optionally further comprise a base as a Part C. [0041] When used, the kit of the present invention comprising a three-part or two-part iodine composition is preferably added to a volume of water to form a dilute molecular iodine solution. Preferably the amount of the acid and base in the iodine composition of the kit is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 after adding the iodine composition to the volume of water. For example, the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] Further features of the present invention are more fully described in the following description of several non-limiting embodiments thereof. This description is included solely for the purposes of exemplifying the present invention. It should not be understood as a restriction on the broad summary, disclosure or description of the invention as set out above. The description will be made with reference to the accompanying drawings in which:
Figure 1 is a graph of iodine conversion efficiency as a function of pH.
Figure 2 is a schematic of a first exemplary flow process for the manufacture of a dilute molecular iodine solution according to the present invention.
Figure 3 is a schematic of a second exemplary flow process for the manufacture of a dilute molecular iodine solution according to the present invention.
DESCRIPTION OF INVENTION
Detailed Description of the Invention
Composition
[0043] Molecular iodine is relatively unstable and readily sublimes, being rapidly lost to the atmosphere through diffusion. Various methods such as complexed iodine (for example iodine attached to a high molecular weight moiety such as povidone (polyvinylpyrrolidone (PVP)) have been developed to produce stable, storable and transportable solution-based compositions of molecular iodine. I2 cannot be concentrated, as the maximum solubility in water is about 330 ppm.
[0044] The inventors have developed an iodine composition, comprising a Part A, a Part B and an optional Part C, which when combined in solution forms molecular iodine. The composition reduces the transport costs of iodine containing compositions for agricultural use. On arrival at the location of application, the iodine solution can be diluted by mixing into a volume of water to form a dilute molecular iodine solution. As the dilution is proceeding, the pH of the solution will change, leading to changes in the concentration of l2. To control this, the present invention provides a two- or three-part iodine solution. The iodine solution comprises an acid and optionally a base to form a buffer, so that the pH is controlled during dilution.
[0045] The present invention provides an iodine composition for agricultural administration, the composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base.
[0046] Preferably, the composition is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base.
[0047] Alternatively, the composition is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid and wherein an optional base is further provided in Part A or B.
[0048] Alternatively, the composition is in the form of a two-part iodine composition, wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid.
[0049] More preferably if the composition is in the form of a two-part iodine composition, the composition comprises: i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide.
[0050] This composition may optionally further comprise a base as a Part C.
[0051] Preferably the acid is a food grade acid, so that the acid does not need to be removed from the agricultural surface (such as the crop surface, agricultural equipment, fruit or vegetable etc), before edible products come into contact with the surface or are consumed by humans or animals. However, in certain embodiments of the invention, non-food grade acids may be acceptable for use. Preferably the acid is able to break down in the soil or water quickly so that the acid does not build up in the soil or water and change the pH over repeated application.
[0052] Preferably the acid is a strong acid. For example, the acid may be sulphuric acid, hydrochloric acid, nitric acid, chloric acid, hydrobromic acid, hydroiodic acid or perchloric acid. More preferably, the strong acid is sulphuric acid.
[0053] Alternatively, the acid may be a weak acid. For example, the acid may be formic acid, acetic acid, benzoic acid, oxalic acid, nitrous acid or sulfurous acid. The weak acid may be a carboxylic acid.
[0054] If a carboxylic acid is used, preferably the carboxylic acid is selected from the group consisting of formic acid, carbonic acid, carbon dioxide hydrate, acetic acid, glycolic acid, glyoxylic acid, oxalic acid, propionic acid, acrylic acid, propiolic acid, lactic acid, 3-hydroxipropionic acid, glyceric acid, pyruvic acid, malonic semialdehyde, mesoxalic semialdehyde, malonic acid, tartronic acid, dihydroxymalonic acid, mesoxalic acid, butyric acid, isobutyric acid, crotonic acid, isocrotonic acid, methacrylic acid, vinylacetic acid, tetrolic acid, 2-hydroxybutyric acid, 3- hydroxybutyric acid, 4-hydroxybutyric acid, a-ketobutyric acid, acetoacetic acid, succinic semialdehyde, succinic acid, methylmalonic acid, fumaric acid, maleic acid, acetylenedicarboxylic acid, malic acid, tartaric acid, oxaloacetic acid, dioxosuccinic acid, valeric acid, isovaleric acid, 2- methylbutiric acid, pivalic acid, p-hydroxyvaleric acid, y-hydroxyvaleric acid, p-hydroxy-p- methylbutyric acid (HMB), glutaric acid, a-ketoglutaric acid, acetonedicarboxylic acid, 2-furoic acid, tetrahydro-2-furoic acid, caproic acid, adipic acid, 2,3-dimethylbutanoic acid, 3,3- dimethylbutanoic acid, citric acid, aconitic acid, isocitric acid, sorbic acid, enanthic acid, pimelic acid, benzoic acid, salicylic acid, 2,2-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4- dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 2,2,3-trimethylbutanoic acid, 2-ethyl-2- methylbutanoic acid, and 2-ethyl-3-methylbutanoic acid. In some embodiments, the carboxylic acid is chosen from the list comprising: citric acid, malic acid, ascorbic acid, acetic acid, oxalic acid, tartaric acid, isocitric acid, citramalic acid, galacturonic acid, shikimic acid, lactic acid, quinic acid, succinic acid, and fumaric acids.
[0055] More preferably, the carboxylic acid is selected from the group consisting of acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, tartaric acid and citric acid. Most preferably the carboxylic acid is citric acid.
[0056] Preferably the optional base is a food grade base, so that the base does not need to be removed from the agricultural surface (such as the crop surface, agricultural equipment, fruit or vegetable etc), before edible products come into contact with the surface or are consumed by humans or animals. However, in certain embodiments of the invention, non-food grade bases may be acceptable for use. Preferably the base is able to break down in the soil or water quickly so that the base does not build up in the soil or water and change the pH over repeated application.
[0057] Preferably the base is a strong base.
[0058] Preferably the base is a hydroxide or carbonate. For example, the base may be sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, or calcium carbonate. More preferably the base is potassium hydroxide or potassium carbonate.
[0059] Preferably the combination of the acid and the base form a buffer system. The formation of molecular iodine from the reaction between the iodate (IO3 ) and iodide (I ) that results in an equilibrium in solution between the triiodide ion (l3 ) and free molecular iodine (I2) / iodide ion (I ) can cause an increase in pH of a solution as acid (H+) is consumed via the formation of water (H2O). The reaction of iodide and iodate in the presence of acid to produce molecular iodine (Dushman reaction) may be expressed in accordance with the following equation:
IO3- + 5h + 6H+ 3I2 + 3H2O
[0060] As explained above, in the presence of iodide ions, molecular iodine exists in a fast equilibrium in solution with triiodide ion, in a reaction that may be expressed as: l2 + I «-> l3-
[0061] Whilst not being held to any theory, it is believed that the amount of l2 that is generated is less than the stoichiometric value according to this equation. When making the dilute molecular iodine solution according to the present invention, it is preferable to use quantities of iodate and iodide which are higher than the stoichiometric quantities. For example, the quantities of iodate and/or iodide may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% higher than the stoichiometric quantities predicted by the above equation. Preferably the quantity of iodate is about 20% higher than the stoichiometric quantities predicted by the above equation (i.e. 120% of the predicted value). Preferably the quantity of iodide is about 50% higher than the stoichiometric quantities predicted by the above equation (i.e. 150% of the predicted value). Preferably the dilute molecular iodine solution according to the present invention is composed with 5% to 20% more iodide than iodate, more preferably 10% to 15% more iodide than iodate.
[0062] The presence of a base, such as sodium hydroxide, as part of a buffering system assists to ensure that, when the iodine composition is mixed with a volume of water to form a dilute molecular iodine solution, the pH of the volume of water and/or the dilute molecular iodine solution is buffered against a rise in pH, and preferably maintains the pH below pH 7.0, more preferably below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6). For example, the pH may be below pH 2 during production of the dilute molecular iodine solution, the adjusted to a pH of 4 to 6 ready for use.
[0063] The pH of the dilute molecular iodine solution is preferably below pH 7.0, 7.5, 6.0, 5.5, 5.0, 4.5, 4.0, 3.5, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.5, 2.4, 2.3, 2.2, 2.1 , 2.0, 1 .9, 1 .8, 1 .7, 1 .6, 1 .5, 1 .4, 1 .3, 1.2, 1.1 , 1.0, 0.9, 0.8, 0.7, 0.6, or 0.5. More preferably the pH is between pH 2.8 and 1.0, more preferably between pH 2.0 and 1 .5, for example pH 1 .6 during production of the dilute molecular iodine solution. In preparing the molecular iodine solution for use, pH of the molecular iodine solution may increase due to dilution. The pH may be adjusted to a pH of 4 to 6 ready for use. Such a pH is less likely to, for example, burn the leaves or tissues of plants to which it applied or change the pH of soil such that the soil microbiota is adversely affected.
[0064] Furthermore, the presence of a base assists to maintain anions in solution, created when protons (H+) derived from the acid are consumed in the Dushman reaction. Without wishing to be bound by theory, it is believed that anions catalyse the formation of molecular iodine and/or assist to push the solutional equilibrium between triiodide and iodine towards the formation of molecular iodine. Therefore, it is believed that the presence of a base serves the dual purpose of buffering against detrimental rises in pH, and catalysing the formation of molecular iodine in preference to triiodide.
[0065] The presence of a base also assists to increase the pH of the dilute molecular iodine solution if the agricultural surface to which the solution is to be applied would be damaged by a very acidic solution. For example, application of a very acidic solution to a plant’s leaves may damage the leaves. In such a case, the pH may be raised (for example above pH 2.0) to avoid acidic burning of the surface. The pH may be adjusted to a pH of 4 to 6 ready for use. [0066] Preferably the iodate is potassium iodate, sodium iodate, magnesium iodate, or calcium iodate. More preferably the iodate is potassium iodate.
[0067] Preferably the iodide is potassium iodide, sodium iodide, magnesium iodide, or calcium iodide. More preferably the iodide is potassium iodide.
[0068] Preferably the iodate is potassium iodate. Preferably the iodide is potassium iodide. Preferably the acid is sulphuric acid. Preferably the base is potassium hydroxide or potassium carbonate. Most preferably the base is potassium hydroxide, the iodate is potassium iodate, the acid is sulphuric acid and the iodide is potassium iodide.
[0069] The or each of the parts of the iodine composition of the present invention may further comprise a polar solvent to form a solution or liquid. For example, the iodine composition may comprise:
- a solution Part A and a dry powder Part B;
- a dry powder Part A and a dry powder Part B;
- a dry powder Part A and a solution Part B;
- a solution Part A and a solution Part B;
- a solution Part A and a dry powder Part B and a solution Part C;
- a dry powder Part A and a dry powder Part B and a solution Part C;
- a dry powder Part A and a solution Part B and a solution Part C;
- a solution Part A and a solution Part B and a solution Part C
- a solution Part A and a dry powder Part B and a dry powder Part C;
- a dry powder Part A and a dry powder Part B and a dry powder Part C;
- a dry powder Part A and a solution Part B and a dry powder Part C; or
- a solution Part A and a solution Part B and a dry powder Part C.
[0070] Preferably if Part C is formed of the base, the Part C is in solid form.
[0071] Where Part A and/or Part B and/or Part C of the iodine composition of the present invention are in the form of a solution comprising a polar solvent, the solution may be a solution in any polar solvent capable of dissolving in sufficient quantities the acid, base and iodate (Part A) or the iodide (Part B) components of the respective Parts, including, but not limited to dimethylsulfoxide (DMSO), dimethylformamide (DMF), lower alkyl alcohols (such as methanol, ethanol, propanol, butanol, ethylene glycol, propanediol, glycerol, etc), acetone, ammonia, dimethyl ether, diethyl ether, tetrahydrofuran, hydroxylamine, acetonitrile, and water, including mixtures of any of the aforementioned polar solvents.
[0072] Preferably, where Part A and/or Part B and/or Part C of the iodine composition of the present invention are in the form of a solution, the solution is a solution in water.
[0073] Part A of the iodine composition contains an iodate. Iodine in its iodate salt form is extremely stable at temperatures below 200°C without a reducing agent and will not decompose until the temperature reaches 500°C.
[0074] Part B of the iodine composition contains an iodide. Iodine in its iodide salt form is very stable.
[0075] Preferably, after being transported to or near to the site where application of molecular iodine is required and prior to application, the Part A and Part B and optional Part C of the iodine composition are added to a volume of water for use. The combination of the Part A and Part B and optional Part C of the iodine composition with the volume of water produces a dilute molecular iodine solution. For example, the Part A and Part B and optional Part C may be added to a volume of water immediately before spraying or otherwise applying the resulting solution to the soil, crop, orchard etc. Preferably on addition of the Part A and Part B and optional Part C to the volume of water, the reaction between the iodate and iodide results in an equilibrium in solution, and the generation of molecular iodine via formation of the triiodide ion, l3 which establishes an equilibrium with free molecular iodine and iodide ion according to the equation: l2 (aq) + h (aq) <=> l3 (aq)
[0076] Preferably on addition of the Part A and Part B and optional Part C to the volume of water to generate the dilute molecular iodine solution, the molecular iodine is present in the dilute molecular iodine solution at from 3 ppm to 330 ppm. For example, the molecular iodine may be present in the dilute molecular iodine solution at 3, 5, 10, 15, 20, 25, 30, 35, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320 or 330 ppm. Preferably the molecular iodine is present in the dilute molecular iodine solution at about 30 ppm (preferably from a 300 ppm preconcentrated solution).
[0077] The preferable amount of molecular iodine present in the dilute molecular iodine solution will depend on the application of the solution. The dilute molecular iodine solution can be used in a range of agricultural applications, by administration to agricultural surfaces. The term “administration to agricultural surfaces” includes injection of the dilute molecular iodine solution into plants or trees. The agricultural surfaces include both man-made surfaces such as machinery, storage facilities and equipment, and food storage and preparation equipment, but also natural surfaces such as plants and soils. [0078] For use as a disinfecting solution (for example disinfection of animal sheds, building, etc.; agricultural product handling equipment and premises; abattoirs and other food processing premises; freezer and cool rooms for agricultural products; nursery plant equipment, racking, seedling trays, etc.) or for use in ground preparation sterilisation/fumigation of soils before the soil is seeded or planted with seedlings, preferably the amount of molecular iodine present in the dilute molecular iodine solution is from 150 ppm to 330 ppm.
[0079] For use as a biocidal folia spray; sterilising dip and fungicidal treatment for seeds, cuttings, runners, tubers etc.; or soil spray for crops, preferably the amount of molecular iodine present in the dilute molecular iodine solution is from 30 ppm to 100 ppm. The dilute molecular iodine solution may also be used as a fungicidal treatment by injection into plants and trees at from 30 ppm to 100 ppm molecular iodine.
[0080] For use as a post-harvest washing solution and fungicidal treatment for fruits, vegetables etc.; sterilising and fungicidal treatment of hydroponic and aeroponic systems; disinfection of animal drinking water, dams, irrigation water and swimming pools, preferably the amount of molecular iodine present in the dilute molecular iodine solution is from 3 ppm to 25 ppm.
[0081] Preferably the amount of acid in the iodine composition is sufficient to maintain the pH of the dilute molecular iodine solution at below pH 5.5, more preferably below pH 2.0. For example, the amount of acid in the iodine composition is preferably sufficient to maintain the pH of the dilute molecular iodine solution at below pH 1 , 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4 or 5.5. More preferably the pH is between pH 2.8 and 1 .0, more preferably between pH 2.0 and 1 .5, for example pH 1 .6. For example, the pH may be below pH 2 during production of the dilute molecular iodine solution, the adjusted to a pH of 4 to 6 ready for use.
[0082] Preferably the amount of base in the iodine composition is sufficient to maintain the pH of the dilute molecular iodine solution at below pH 5.5, more preferably below pH 2.0. For example, the amount of base in the iodine composition is preferably sufficient to maintain the pH of the dilute molecular iodine solution at below pH 1 , 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4 or 5.5. More preferably the pH is between pH 2.8 and 1 .0, more preferably between pH 2.0 and 1.5, for example pH 1.6. For example, the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
[0083] The feature of maintenance of the pH of the dilute molecular iodine solution after mixing the iodine composition comprising a Part A and a Part B and optional Part C with a volume of water is important to ensure that the molecular iodine remains in solution. The iodine composition will be mixed by the user (farmer, orchardist etc) with the water that is available. Generally, the total dissolved solids (TDS) of water used in agriculture is less than 1000 ppm, as higher salt concentrations are not suitable for growing. However, depending on the available water, the types of salts and/or the type of crop being grown, the TDS may be higher than 1000 ppm.
[0084] The present iodine composition is designed to be used with water in the pH range from 5.7 to 8.3. The presence of an acid and a base in the iodine composition of the present invention is designed to provide a buffer in such conditions. For example, if the user is combining the iodine composition with water at pH 8.3, the pH can be maintained at 2.0 or lower by the presence of the acid and the base. If the user is combining the iodine composition with water at pH 5.7, the pH can be maintained at 2.0 or lower by the presence of the and the base. If the pH of the available water for dilution is outside the range of 5.7 to 8.3, the pH of the water may be first adjusted to within the range by adding a separate acid or base to the water before adding the iodine composition of the present invention.
[0085] In some situations, it is possible that the water at the site of mixing and application is “hard” water, i.e., water with large amounts of dissolved minerals, particularly calcium and magnesium. Water hardness is the measurement of the amount of divalent cations dissolved in the tested water and is, therefore, related to total dissolved solids. The more divalent cations (calcium and magnesium carbonates, bicarbonates and sulfates) dissolved in the water the "harder" the water. Such hard water is often alkaline. This may interfere with the ability of the acid and/or base to buffer the dilute molecular iodine solution to a suitable pH, as the acid will interact with the dissolved minerals and be neutralised. Therefore, sufficient acid and base must be present in the iodine composition to react with any alkaline hardness in the water and still maintain the dilute molecular iodine solution at a pH of from pH 2 to 6 (more preferably lower than pH 5.5, lower than pH 2.0, for example a pH of about 1 .6). For example, the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
[0086] Preferably the pH of the dilute molecular iodine solution is below pH 5.5, below pH 5 or below pH 4.5. More preferably the amount of acid and base in the iodine composition is sufficient to maintain the pH of the dilute molecular iodine solution at below pH 2.0 (for example a pH of about 1 .6). For example, the pH may be below pH 2 during production of the dilute molecular iodine solution, then adjusted to a pH of 4 to 6 ready for use.
[0087] In order to push the Dushman reaction towards the generation of molecular iodine, an excess of iodate and iodide (i.e. more than would be required to generate the maximum concentration of 330 ppm of molecular iodine) is provided in the iodine composition and the dilute molecular iodine solution. Furthermore, there is preferably an excess of iodide to iodate (KI > KIOs) in the iodine composition and the dilute molecular iodine solution. In this case, the iodide consumes all of the iodate in the reaction to generate molecular iodine, to reduce the amount of free unreacted iodate that could form triiodide. [0088] Preferably the ratio of iodide to iodate in the dilute molecular iodine solution is from 10:0.5 to 5:1 (molar). Most preferably the ratio of iodide to iodate in the dilute molecular iodine solution is 5:1.2 (molar).
[0089] Preferably the ratio of iodide to iodate in the dilute molecular iodine solution is from 5:0.5 to 4:1 (weight). Most preferably the ratio of iodide to iodate in the dilute molecular iodine solution is 3.88:1.2 (weight).
[0090] Preferably the dilute molecular iodine solution according to the present invention is composed with 5% to 20% more iodide than iodate, more preferably 10% to 15 more iodide than iodate.
[0091] The Parts of the iodine compositions may be in the form of dry powders, or may be liquids. In one example, the iodine is a two-part composition, with Part A in the form of a liquid comprising iodate and an acid, and Part be in the form of a liquid comprising iodide. In another example, Part A of the iodine composition may be in the form of a dry powder comprising an iodate and an acid, Part B may be in the form of a liquid comprising an iodide, and Part C may be in the form of a dry powder comprising a base.
Table 1 : Example components for dilute molecular iodine solutions
Figure imgf000021_0001
Figure imgf000022_0001
Method of Treating Agricultural Surfaces
[0092] The addition of molecular iodine to agricultural surfaces, including plants and soil, has a number of benefits. The presence of molecular iodine may:
- control pests and pathogens of soil and plants, including bacterial and fungal pathogens and nematodes;
- improve plant growth by, for example, increasing biomass and/or increasing the levels of antioxidants in the plants;
- increase the level of iodine in plant biomass; and/or
- reduce methane production in ruminant livestock raised on molecular iodine-treated biomass feed, thereby reducing greenhouse gas production associated with livestock agriculture, with concomitant reductions in global warming effects arising from methane emissions.
[0093] The iodine composition of the present invention may be diluted with water or other solvents before application; preferably the iodine composition is dissolved or diluted in water to form a dilute molecular iodine solution before application to agricultural surfaces, including plants and soil.
[0094] The dilute molecular iodine solutions may be used on agricultural surfaces in roles such as:
- disinfecting solutions (for example disinfection of animal sheds, building, etc.; agricultural product handling equipment and premises; abattoirs and other food processing premises; freezer and cool rooms for agricultural products; nursery plant equipment, racking, seedling trays, etc.);
- ground preparation sterilisation/fumigation of soils before the soil is seeded or planted with seedlings;
- biocidal folia spray;
- injection into plants or trees;
- sterilising dip for seeds, cuttings, runners, tubers etc.;
- soil spray for crops; - post-harvest washing solution for fruits, vegetables etc.;
- sterilising of hydroponic and aeroponic systems;
- disinfection of animal drinking water, dams, irrigation water and swimming pools.
[0095] The present invention therefore provides a method to control agricultural pathogens using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6). Preferably the pathogens are soil, plant or animal agricultural pathogens.
[0096] Alternatively, the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of the acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1 .6).
[0097] The present invention also provides a method to control agricultural pathogens using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the agricultural surface wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the volume of water to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
[0098] Preferably the dilute molecular iodine solution is administered at a rate of 500 L/ha to 5,000 L/ha of land area to which it is applied. For example, application rates when used as a soil steriliser/fumigant (pre-plant or pre-seeding) would be from 500 and 5000 L/ha. Application rates when used as a fungicide/biocide would vary between 500 and 2,500 L/ha. Application rates when used as a soil drench would be based on type of irrigation and amount of the formulation required to saturate root zone of the plant, but preferably less than 5,000 L/ha.
[0099] Preferably the molecular iodine is present at a concentration of from 150 ppm to 320 ppm in at least the top layer of soil after application of the dilute molecular iodine solution. For example, when the dilute molecular iodine solution is administered as a steriliser/fumigant, preferably the concentration is at least 300 ppm in at least the top layer of soil after application. When the dilute molecular iodine solution is administered as a folia spray, preferably the concentration is from 30 ppm to 150 ppm in at least the top layer of soil after application. When the dilute molecular iodine solution is administered as a soil drench, preferably the concentration is from 30 ppm to 150 ppm in at least the top layer of soil after application. [00100] Examples of agricultural pathogens, such as those of soil and plants, controlled by use of the present invention include: fungi (including Fusarium sp., Rhizoctonia sp., Sclerotinia sclerotium, Botrytis spp., Colletotrichum spp.), oomycetes (including Pythium sp., Phytophthora cinnamomi), bacteria (including mollicutes, Zymomonas sp., Erwinia sp., Agrobacterium sp., Xanthomonas campestris, Pseudomonas syringae), algae (including parasitic green algae), protozoa, nematodes, arthropods (including thrips, aphids, mites, and ticks), viruses, and viroids.
[00101] The present invention further provides a method to improve plant growth using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
[00102] Alternatively, the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
[00103] The present invention further provides a method to improve plant growth using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
[00104] Preferably the improvement in plant growth is a result of increasing biomass and/or increasing the levels of antioxidants in the plants, and/or reducing, limiting or eliminating the deleterious effects of soil and/or plant pathogens and/or pests.
[00105] The present invention further provides a method to increase the level of iodine in plant biomass using a three-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
[00106] Alternatively, the composition of the method is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid wherein an optional base is further provided in Part A or B, and wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
[00107] The present invention also provides a method to increase the level of iodine in plant biomass using a two-part iodine composition, said method comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; c) administering the resulting dilute molecular iodine solution to the plants and soil wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid wherein the amount of acid and base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 (preferably a pH of about 1.6).
[00108] Application to plants and/or soil may be in the form of a spray applied using a pump-pack, hand spray or boom spray; applied using a hose or jet or crop-duster equipped aircraft; and through watering systems, i.e., trickle, mini sprinklers, flood irrigation, etc. The solution may further be injected into plants or trees,
[00109] If the dilute molecular iodine solution is administered to an agricultural surface such as soil, plants, seeds, trees etc, the results plant on growing may be biofortified with a greater amount of iodine in its tissues than one grown in the absence of the dilute molecular iodine solution of the present invention. The dilute molecular iodine solution may be administered to an agricultural surface such as soil, plants, seeds, trees etc. for control of agricultural pathogens, improvement in plant growth, an increase in the level of iodine in plant biomass and/or a reduction in methane production in ruminant livestock.
Excipients
[001 10] The iodine composition of the present invention and/or dilute molecular iodine solution of the present invention may further comprise one or more of the following auxiliary components: inert carrier(s), surface active agent(s) such as a sticker or spreader, stabilizer(s) and/or dye(s). The iodine composition may also be suspended in a carrier fluid, such as air, nitrogen, carbon dioxide or fumigant gas. The iodine composition and/or dilute molecular iodine solution may comprise auxiliaries such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, frost protectants, biocides, thickeners and/or other auxiliaries, such as adjuvants, for example. An adjuvant in this context is a component which enhances the biological effect of the iodine composition and/or dilute molecular iodine solution, without the component itself having a biological effect. Examples of adjuvants are agents which promote the retention, spreading, attachment to the leaf surface, or penetration of the iodine composition and/or dilute molecular iodine into the soil. Generally speaking, the iodine composition and/or dilute molecular iodine solution may be combined with any solid or liquid additive commonly used for formulation purposes. [001 11 ] Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic or pseudoplastic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), colour (dyes/pigment dispersions), wash-off (film formers or sticking agents), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
Kits
[001 12] The present invention provides a kit for the formation of molecular iodine comprising: a) an iodine composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base; and b) instructions for use.
[001 13] The kit for the formation of molecular iodine preferably comprises: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base b) instructions for use.
[001 14] The kit for the formation of molecular iodine may alternatively comprise: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate; ii. Part B comprises: an iodide; and iii. Part C comprises: an acid b) instructions for use wherein an optional base is provided in Part A or B.
[001 15] The kit for the formation of molecular iodine may alternatively comprise: a) a two-part iodine composition, wherein: i. Part A comprises: an iodate, an acid and an optional base; and ii. Part B comprises: an iodide or i. Part A comprises: an iodate; and ii. Part B comprises: an iodide, an acid and an optional base or i. Part A comprises: an iodate and an acid; and ii. Part B comprises: an iodide and an optional base or i. Part A comprises: an iodate and an optional base; and ii. Part B comprises: an iodide and an acid b) instructions for use.
[001 16] When used, the kit preferably results in a composition for agricultural administration of molecular iodine. The composition of the kit may be used for control of agricultural pathogens, improvement in plant growth, an increase in the level of iodine in plant biomass and/or a reduction in methane production in ruminant livestock.
[001 17] When used, the kit of the present invention comprising a three-part or two-part iodine composition is preferably added to a volume of water to form a dilute molecular iodine solution. Preferably the amount of acid and base in the iodine composition of the kit is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5, more preferably below pH 2.0 after adding the iodine composition to the volume of water.
General
[001 18] Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. The invention includes all such variation and modifications. The invention also includes all of the steps, features, formulations and compounds referred to or indicated in the specification, individually or collectively and any and all combinations or any two or more of the steps or features.
[001 19] Each document, reference, patent application or patent cited in this text is expressly incorporated herein in their entirety by reference, which means that it should be read and considered by the reader as part of this text. That the document, reference, patent application or patent cited in this text is not repeated in this text is merely for reasons of conciseness.
[00120] Any manufacturer’s instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be employed in the practice of the invention.
[00121 ] The present invention is not to be limited in scope by any of the specific embodiments described herein. These embodiments are intended for the purpose of exemplification only. Functionally equivalent products, formulations and methods are clearly within the scope of the invention as described herein.
[00122] The invention described herein may include one or more range of values (e.g. size, displacement and field strength etc). A range of values will be understood to include all values within the range, including the values defining the range, and values adjacent to the range which lead to the same or substantially the same outcome as the values immediately adjacent to that value which defines the boundary to the range. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. Hence “about 80 %” means “about 80 %” and also “80 %”. At the very least, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
[00123] Throughout this specification, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers. It is also noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as “comprises”, “comprised”, “comprising” and the like can have the meaning attributed to it in U.S. Patent law; e.g., they can mean “includes”, “included”, “including”, and the like; and that terms such as “consisting essentially of’ and “consists essentially of’ have the meaning ascribed to them in U.S. Patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention. [00124] Other definitions for selected terms used herein may be found within the detailed description of the invention and apply throughout. Unless otherwise defined, all other scientific and technical terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the invention belongs. The term “active agent” may mean one active agent, or may encompass two or more active agents.
[00125] The following examples serve to more fully describe the manner of using the abovedescribed invention, as well as to set forth the best modes contemplated for carrying out various aspects of the invention. It is understood that these methods in no way serve to limit the true scope of this invention, but rather are presented for illustrative purposes.
EXAMPLES
[00126] Further features of the present invention are more fully described in the following nonlimiting Examples. This description is included solely for the purposes of exemplifying the present invention. It should not be understood as a restriction on the broad description of the invention as set out above.
Example 1
Measurement of Molecular Iodine
[00127] Because of the numerous forms that molecular iodine can exist in and its volatility, there is no practical way to measure all forms simultaneously. However, measuring systems are available to assess and measure relevant iodine species.
Total I: It is generally accepted that the ICP/MS system with an alkaline digest of soil and liquid samples is the best for the measurement of total iodine.
Sodium Thiosulphate Titration: A common, simple form of measuring molecular iodine is by sodium thiosulphate titration. The principle used is that, as iodine reacts with sodium thiosulphate (the oxidant) it is reduced to form iodide, and that iodine reacts with starch to form a dense blue colour. By reacting iodine in the presence of starch with a known volume and concentration of thiosulfate, an end point is reached when the blue suddenly disappears. This technique measures both l2 and l3’.
Photometric Measurement: A portable photometric for measuring molecular iodine in the range 0 to 12.5 ppm.
Iodine Test Paper/Strips: These comprise a colour reaction for the presence of molecular iodine in increments of from 5 to 50 ppm.
Iodine Gas Detector: These measure molecular iodine in ranges of 0 to 2 ppm and 0 to 20 ppm.
Example 2
Exemplary Iodine Solutions
ISQL300
[00128] Product requirements for 1000 litres as follows:
Potassium iodide: 300/0.917*150% 491 g
Potassium iodate: 491/3.88*120% 151.8 g
Citric acid 5000 g
Sodium Hydroxide 500 g
Source water 996.4 litres [00129] ISOL 300 dilute iodine solution is made using ISOL300/A, ISOL300/B, ISOL300/C and water. The dilute molecular iodine solution has a pH of approx. 4.5 and an iodate (IO3 ) to iodide (I ) ratio of 5:1 .2 (molar) or 3.88:1 .2 (weight).
ISOL300/A: potassium iodate powder
ISOL300/B: x100 concentrated solution comprising 4.907 kgs potassium iodide and 50 kgs citric acid mixed with water to make up 100 litres
ISOL300/C: anhydrous sodium hydroxide granules
[00130] Mixing (1000 litres): Start with 996.4 of water in a mixing tank and remove two 5 L amounts. Water in main tank should be continually circulated. To one of the 5 L lots of water add the iodate or ISOL300/A and mix until fully dissolved, add this to the main tank. Then add the ISOL300/B. To the other 5 L lot of water, add the ISOL300/C and mix until fully dissolved, add to main tank. The solution is ready to use after 10 to 15 mins.
Table 2: To makeup different amounts of solution at 300 ppm, the following is required
Figure imgf000034_0001
ISOL10Q
[00131 ] Product requirements for 1000 litres as follows:
Potassium iodide: 100/0.917*150% 163.6 g
Potassium iodate: 163.6/3.88*120% 50.6 g
Citric acid 4000 g
Sodium Hydroxide 500 g
Source water 997.2 litres
[00132] ISOL 100 dilute iodine solution is made using ISOL100/A, ISOL100/B, ISOL100/C and water. The dilute molecular iodine solution has a pH of approx. 4.5 and an iodate (IO3 ) to iodide (I ) ratio of 5:1 .2 (molar) or 3.88:1 .2 (weight).
ISOL100/A: potassium iodate powder
ISOL100/B: x100 concentrated solution comprising 1.636 kgs potassium iodide and 40 kgs citric acid mixed with water to make up 100 litres
ISOL100/C: anhydrous sodium hydroxide granules [00133] Mixing (1000 litres): Start with 997.2 L of water in a mixing tank and remove two 5 L amounts. Water in main tank should be continually circulated. To one of the 5 L lots of water add the iodate or ISOL100/A and mix until fully dissolved, add this to the main tank. Then add the ISOL100/B. To the other 5 L lot of water, add the ISOL100/C and mix until fully dissolved, add to main tank. The solution is ready to use after 10 to 15 mins.
Table 3: To makeup different amounts of solution at 100 ppm, the following is required
Figure imgf000035_0001
ISOL25
[00134] Product requirements for 1000 litres as follows:
Potassium iodide: 25/0.917*150% 40.9 g
Potassium iodate: 40.9/3.88*120% 12.65 g
Citric acid 4000 g
Sodium Hydroxide 500 g
Source water 997.2 litres
[00135] ISOL 25 dilute iodine solution is made using ISOL25/A, ISOL25/B, ISOL25/C and water. The dilute molecular iodine solution has a pH of approx. 4.5 and an iodate (IO3 ) to iodide (I ) ratio of 5:1 .2 (molar) or 3.88:1 .2 (weight).
ISOL25/A: potassium iodate powder
ISOL25/B: x100 concentrated solution comprising 409g potassium iodide and 40 kgs citric acid mixed with water to make up 100 litres
ISOL25/C: anhydrous sodium hydroxide granules
[00136] Mixing (1000 litres): Start with 997.2 L of water in a mixing tank and remove two 5 L amounts. Water in main tank should be continually circulated. To one of the 5 L lots of water add the iodate or ISOL100/A and mix until fully dissolved, add this to the main tank. Then add the ISOL100/B. To the other 5 L lot of water, add the ISOL100/C and mix until fully dissolved, add to main tank. The solution is ready to use after 10 to 15 mins. Table 4: To makeup different amounts of solution at 25 ppm, the following is required
Figure imgf000036_0001
Example 3
Use of Dilute Molecular Iodine Solutions
Table 5: Use of dilute molecular iodine solutions for the treatment of various agricultural pathogens
Figure imgf000036_0002
Example 4
Exemplary Iodine Solutions 30 ppm strength - ISOL30
[00137] Product requirements for 1000 litres as follows:
Add 1 .2 L of ISOL A with 1 .0 L of ISOL B to 97.8 L source water.
ISOL A: potassium iodate 8.5 g dissolved in 1 .2 L of 20% (w/w) sulfuric acid and
ISOL B: potassium iodide 37.8 g dissolved in 1 L of source water (KI cone = 37.8g/L)
Mix and allow reaction to occur for 10 minutes
Add 900 L of source water
Adjust pH with 400 g of potassium carbonate to pH>4
30 ppm strength - ISOL30
[00138] Product requirements for 1000 litres as follows:
Add 1 .2 L of ISOL A with 0.4 L of ISOL B to 98.4 L source water.
ISOL A: potassium iodate 8.5 g dissolved in 1 .2 L of 20% (w/w) sulfuric acid and
ISOL B: potassium iodide 37.8 g dissolved in 0.4 L of source water (KI cone = 94.5g/L)
Mix and allow reaction to occur for 10 minutes
Add 900 L of source water
Adjust pH with 400 g of potassium carbonate to pH>4
[00139] The ISOL A and ISOLB are added to a small volume of water (about 10 L or 10% of final volume) to generate molecular iodine at about 300 ppm and about pH 1 .6 (or at least below pH 2). After 10 minutes, the small volume of water is topped up to a final volume of 1000 L (10- fold dilution) to produce a 30 ppm dilute molecular iodine solution at about pH 2.5.
[00140] The pH of the dilute molecular iodine solution may be adjusted to about pH >4 (pH 4 to 6) with a base. The base (for example a hydroxide or carbonate of sodium or potassium) is provided in solid form to reduce further dilution of the dilute molecular iodine solution.
Example 5
Use of Exemplary Iodine Solutions in trials able 6: Use of exemplary iodine solutions in trials
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001

Claims

1. An iodine composition for agricultural administration of molecular iodine, the composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base.
2. The composition of claim 1 wherein the iodine composition is in the form of a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base.
3. The composition of claim 1 wherein: a) the acid is sulphuric acid; b) the iodate is potassium iodate; and/or c) the iodide is potassium iodide.
4. The composition of claim 2 wherein the optional base is potassium hydroxide or potassium carbonate.
5. A method to produce a dilute molecular iodine solution of claim 2, comprising the step of adding the Part A and Part B to a volume of water, and then adding optional Part C of the iodine composition the volume of water.
6. The method of claim 5 wherein the pH of the dilute molecular iodine solution is below pH 5.5.
7. A method to control agricultural pathogens using the iodine composition of claim 1 , said method comprising the steps of: a) adding the iodate, iodide and acid to a volume of water to form a dilute molecular iodine solution; b) optionally adding a base to the volume of water; and c) administering the resulting dilute molecular iodine solution to the agricultural surface wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5.
8. The method of claim 7 comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) optionally adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the agricultural surface wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of the acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5.
9. A method to improve plant growth using the iodine composition of claim 2, said method comprising the steps of: a) adding the iodate, iodide, and acid to a volume of water to form a dilute molecular iodine solution; b) optionally adding a base to the volume of water; and c) administering the resulting dilute molecular iodine solution to the agricultural surface wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5.
10. The method of claim 9 comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) optionally adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein
I. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5.
11. A method to increase the level of iodine in plant biomass using the composition of claim 1 , said method comprising the steps of: a) adding the iodate, iodide, and acid to a volume of water to form a dilute molecular iodine solution; b) optionally adding a base to the volume of water; and c) administering the resulting dilute molecular iodine solution to the agricultural surface wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5.
12. The method of claim 11 comprising the steps of: a) adding Part A of the iodine composition to a volume of water and mixing; b) adding Part B of the iodine composition to the volume of water and mixing; and c) optionally adding Part C of the iodine composition to the volume of water and mixing; d) administering the resulting dilute molecular iodine solution to the plants and soil wherein i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide; and iii. Part C comprises: a base wherein the amount of acid and optional base added to the volume of water is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5.
13. A kit for the formation of molecular iodine comprising: a) an iodine composition comprising: i. an iodate; ii. an iodide; iii. an acid; and optionally iv. a base; and b) instructions for use. The kit of claim 13 wherein the iodine composition is: a) a three-part iodine composition, wherein: i. Part A comprises: an iodate and an acid; ii. Part B comprises: an iodide and an acid; and iii. Part C comprises: a base b) instructions for use. The kit of claim 13 wherein when used, the iodine composition is added to a volume of water to form a dilute molecular iodine solution. The kit of any claim 13, wherein the amount of acid and optional base in the iodine composition of the kit is sufficient to adjust the pH of the dilute molecular iodine solution to below pH 5.5 after adding the iodine composition to a volume of water.
PCT/AU2023/050360 2022-05-19 2023-05-01 Iodine solution WO2023220772A1 (en)

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