Classifications

• • A23L3/3508—
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
  • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
  • A23B2/729—Organic compounds; Microorganisms; Enzymes
  • A23B2/742—Organic compounds containing oxygen
  • A23B2/754—Organic compounds containing oxygen containing carboxyl groups
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B11/00—Preservation of milk or dairy products
  • A23B11/10—Preservation of milk or milk preparations
  • A23B11/18—Preservation of milk or milk preparations by addition of preservatives
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/50—Preservation of foods or foodstuffs, in general by irradiation without heating
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
  • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
  • A23B2/729—Organic compounds; Microorganisms; Enzymes
  • A23B2/742—Organic compounds containing oxygen
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
  • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
  • A23B2/788—Inorganic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B4/00—Preservation of meat, sausages, fish or fish products
  • A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
  • A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
  • A23B4/20—Organic compounds; Microorganisms; Enzymes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B4/00—Preservation of meat, sausages, fish or fish products
  • A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
  • A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
  • A23B4/24—Inorganic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B5/00—Preservation of eggs or egg products
  • A23B5/08—Preserving with chemicals
  • A23B5/12—Preserving with chemicals in the form of liquids or solids
  • A23B5/14—Organic compounds; Microorganisms; Enzymes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B5/00—Preservation of eggs or egg products
  • A23B5/08—Preserving with chemicals
  • A23B5/12—Preserving with chemicals in the form of liquids or solids
  • A23B5/18—Inorganic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
  • A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
  • A23B7/153—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of liquids or solids
  • A23B7/154—Organic compounds; Microorganisms; Enzymes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
  • A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
  • A23B7/153—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of liquids or solids
  • A23B7/157—Inorganic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B9/00—Preservation of edible seeds, e.g. cereals
  • A23B9/16—Preserving with chemicals
  • A23B9/24—Preserving with chemicals in the form of liquids or solids
  • A23B9/26—Organic compounds; Microorganisms; Enzymes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B9/00—Preservation of edible seeds, e.g. cereals
  • A23B9/16—Preserving with chemicals
  • A23B9/24—Preserving with chemicals in the form of liquids or solids
  • A23B9/30—Inorganic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L19/00—Products from fruits or vegetables; Preparation or treatment thereof
  • A23L19/10—Products from fruits or vegetables; Preparation or treatment thereof of tuberous or like starch containing root crops
  • A23L19/105—Sweet potatoes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L19/00—Products from fruits or vegetables; Preparation or treatment thereof
  • A23L19/10—Products from fruits or vegetables; Preparation or treatment thereof of tuberous or like starch containing root crops
  • A23L19/12—Products from fruits or vegetables; Preparation or treatment thereof of tuberous or like starch containing root crops of potatoes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
  • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation

Definitions

• the present invention is generally directed to compositions and methods that can be used to, among other things, protect foodstuffs and agricultural products from decay.
• the methods in accordance with some embodiments of the invention comprise contacting the edible matter, or a substrate therefor, with performic acid.
• the performic acid is provided as part of a composition containing performic acid, and while some such compositions per se are known, there are provided in accordance with embodiments of the invention novel such compositions, as well as processes for making such novel compositions.
• a method comprising contacting edible matter or a substrate therefor with a composition comprising performic acid.
• a method for protecting edible matter from decay comprising contacting edible matter or a substrate therefor with a composition comprising performic acid for a time and in an amount and/or at a concentration sufficient to protect said edible matter from said decay.
• a method for killing weeds or foliage comprising contacting an area in which weeds grow with a composition comprising performic acid or a performic acid source and an oxidizer for a time and in an amount and/or at a concentration sufficient to kill said weeds or foliage or to prevent their growth.
• the composition is such that at a concentration of 20 ppm performic acid and a contact time of one minute at room temperature, the composition achieves a 10,000-fold (4 log) reduction in the colony forming units (cfu) of a pathogen grown on a designed growth medium, wherein the pathogen is at least one of the pathogens in the group consisting of Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), Enterococcus hirae (ATCC 10541), Candida albicans (ATCC 10231), Aspergillus niger (ATCC 16404) and Penecillium w.t.
• Escherichia coli ATCC 8739
• Staphylococcus aureus ATCC 6538
• Pseudomonas aeruginosa ATCC 9027
• Enterococcus hirae ATCC 10541
• the composition is such that at a concentration of 20 ppm performic acid and a contact time of one minute at room temperature, the composition achieves a 100,000-fold (5 log) reduction in the cfu of a pathogen grown on a designed growth medium, wherein the pathogen is at least one of the pathogens in the group consisting of Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), Enterococcus hirae (ATCC 10541).
• ATCC 8739 Escherichia coli
• Staphylococcus aureus ATCC 6538
• Pseudomonas aeruginosa ATCC 9027
• Enterococcus hirae ATCC 10541.
• the composition meets or exceeds at least one of the following Standards: BS EN 1276:1997, BS EN 1650:1998, BS EN 13697:2001, BS EN 1276:2009. In some embodiments, the composition exceeds at least one of Standard BS EN 1276:1997 or Standard BS EN 1276:2009. In some embodiments, the composition possesses bactericidal activity within one minute at 20° C. under dirty conditions of 3.0 g/l bovine albumin for at least one of the reference strains E.
• the composition possesses bactericidal activity within one minute at 20° C. under dirty conditions of 3.0 g/l bovine albumin for the reference strains E. coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), and Enterococcus hirae (ATCC 10541).
• the composition exceeds at least one of Standard BS EN 1650:1998 and Standard BS EN 13697:2001.
• the composition possesses fungicidal activity within one minute at 20° C. under dirty conditions of 3.0 g/l bovine albumin for at least one of the reference strains Candida albicans, Aspergillus brasiliensis ( Aspergillus niger ), and Penecilium w.t.
• the composition possesses fungicidal activity within one minute at 20° C.
• the composition exceeds Standard BS EN 13697:2001.
• the composition is a composition according to any one of original claims 61 to 106 or a composition in accordance with embodiment of the invention.
• the edible matter is selected from the group consisting of fruits, vegetables, grains, sprouts, nuts, seeds, meats, meat products, milk, milk products, fish, poultry, eggs, and mixtures thereof.
• the edible matter is selected from the group consisting of apple, avocado, citrus—mandarin, citrus—orange, citrus—mineola, citrus—grapefruit, citrus—lemon, date, kiwi, lychee, mango, peach, pear, persimmon, pomegranate, pepper, asparagus, banana, broccoli, cabbage, carrot, cauliflower, celery, corn, kohlrabi, cucumber, eggplant, garlic, lettuce, onion, peanut, potato, strawberry, sweet pepper, sweet potato, tomato, watermelon, and grape.
• the edible matter is not fully cooked, e.g. the edible matter is uncooked or only partially cooked.
• said composition kills at least one of a strain of bacteria, a fungus, a yeast, a virus, and an algae, a mold, protozoa, an amoeba, and spore-propagating microorganisms.
• said bacteria is selected from the group consisting of gram-positive bacteria.
• said gram-positive bacteria are selected from the group consisting of Staphylococcus, Streptococcus, Enterococcus, Bacillus, Corynebacterium, Nocardia, Clostridium, Actinobacteria and Listeria.
• said bacteria is selected from the group consisting of gram-negative bacteria.
• said gram-negative bacteria are selected from the group consisting of Escherichia, Salmonella, Shigella, Enterobacteriaceae, Pseudomonas, Moraxella, Helicobacter, Stenotrophomonas, Bdellovibrio, acetic acid bacteria, Legionella, cyanobacteria, spirochaetes, green sulfur bacteria, green non-sulfur bacteria, and respiratory symptoms Moraxella.
• said bacteria is selected from the group consisting of Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Enterococcus hirae.
• said fungus is selected from the group consisting of Magnaporthe, Ophiostoma, Cryphonectria, Fusarium, Ustilago, Alternaria, Cochliobolus, Aspergillus, Candida, Cryptococcus, Histoplasma, and Pneumocytis.
• said yeast is selected from the group consisting of Cryptococcus neoformans, Candida albicans, Candida tropicalis, Candida stellatoidea, Candida glabrata, Candida krusei, Candida parapsilosis, Candida guilliermondii, Candida viswanathii, Candida lusitaniae and Rhodotorula mucilaginosa.
• said virus is selected from the group consisting of Adenoviruses, Herpesviruses, Poxviruses, Parvoviruses, Reoviruses, Picornaviruses, Togaviruses, Orthomyxoviruses, Rhabdoviruses, Retroviruses and Hepadnaviruses.
• said composition kills at least one of an insect, an arachnid and a nematode.
• said insect is selected from the group consisting of Blattodea, Coleoptera, Dermaptera, Diptera, Embioptera, Grylloblattaria, Hymenoptera, Lepidoptera, Mantodea, Mecoptera, Megaloptera, Neuroptera, Orthoptera, Phasmatodea, Phthiraptera, Plecoptera, Siphonaptera, Strepsiptera, Trichoptera, Zoraptera, Zygentoma, Ephemeroptera, Odonata, Thysanura, Monura, and Archaeognatha.
• said insect is an immature insect. In some embodiments, said insect is in the egg stage, the larval stage or the pupal stage. In some embodiments, said insect is a mature insect. In some embodiments, said arachnid is a member of the group Acarina.
• said nematode is selected from the group consisting of Ascaris, Filaria, Ancylostoma, and Necator, Enterobius Trichuris, Trichinella, Baylisascaris, Dirofilaria, Haemonchus, Aphelenchoides, Ditylenchus, Globodera, Heterodera, Longidorus, Meloidogyne, Nacobbus, Pratylenchus, Trichodorus, Xiphinema and Bursaphelenchus.
• by said contacting said composition kills a rodent. In some embodiments, by said contacting said composition kills a weed or foliage or prevents its growth.
• the mass of performic acid (PFA) which is contacted with said edible matter or substrate therefor is not more than 0.001 times the mass of the edible matter or substrate therefor. In some embodiments, the mass of PFA which is contacted with said edible matter or substrate therefor is not more than 0.0001 times the mass of the edible matter or substrate therefor. In some embodiments, the mass of PFA which is contacted with said edible matter or substrate therefor is not more than 0.00001 times the mass of the edible matter or substrate therefor.
• the ratio of the mass of PFA which is contacted with said edible matter or substrate therefor to the surface area of said edible matter or substrate therefor is not more than 1 mg per 100 cm 2 . In some embodiments, the ratio of the mass of PFA which is contacted with said edible matter or substrate therefor to the surface area of said edible matter or substrate therefor is not more than 1 mg per 500 cm 2 . In some embodiments, the ratio of the mass of PFA which is contacted with said edible matter or substrate therefor to the surface area of said edible matter or substrate therefor is not more than 1 mg per 1000 cm 2 .
• the ratio of the mass of PFA which is contacted with said edible matter or substrate therefor to the surface area of said edible matter or substrate therefor is not more than 1 mg per 5000 cm 2 . In some embodiments, the ratio of the mass of PFA which is contacted with said edible matter or substrate therefor to the surface area of said edible matter or substrate therefor is not more than 1 mg per 10000 cm 2 . In some embodiments, the ratio of the mass of the PFA which is contacted with said edible matter or substrate therefor to the volume of said edible matter or substrate therefor is not more than 1 g per 0.1 m 3 .
• the ratio of the mass of the PFA which is contacted with said edible matter or substrate therefor to the mass of said edible matter or substrate therefor is not more than 1 g per 0.3 m 3 . In some embodiments, the ratio of the mass of the PFA which is contacted with said edible matter or substrate therefor to the mass of said edible matter or substrate therefor is not more than 1 g per 0.5 m 3 . In some embodiments, the ratio of the mass of the PFA which is contacted with said edible matter or substrate therefor to the mass of said edible matter or substrate therefor is not more than 1 g per 1 m 3 .
• the PFA is brought into contact with said edible matter by immersing the edible matter in the composition. In some embodiments, the PFA is brought into contact with said edible matter by spraying the composition on said edible matter. In some embodiments, the PFA is brought into contact with said edible matter by fogging the edible matter with the composition. In some embodiments, the PFA is in the gas phase when it is brought into contact with said edible matter. In some embodiments, the PFA is generated in the fog or the gas phase by creating a PFA source-containing fog or gas, and bringing said PFA source-containing fog or gas into contact with ozone in the presence of said edible matter. In some embodiments, said ozone in gaseous. In some embodiments, said ozone is dissolved in water.
• the performic acid is brought into contact with a substrate for the edible matter, which is subsequently brought into contact with said edible matter.
• the composition is prepared in accordance with any of original claims 107 to 111 .
• the edible matter is not a plant oil that is still in edible form.
• the edible matter is not fully cooked, e.g. the edible matter is uncooked or only partially cooked.
• an aqueous composition containing (1) water, (2) at least one of (a) phosphonic acid (HP(O)(OH) 2 ) or a salt thereof and (b) phosphoric acid, (3) a carboxylic acid, (4) a surfactant, and (5) at least one of a performic acid source and an oxidizer which can oxidize said performic acid source to performic acid.
• the carboxylic acid is present in a concentration of 0.5 to 42 wt. %. In some embodiments, the carboxylic acid is present in a concentration of 0.5 to 1 wt. %. In some embodiments, the carboxylic acid is present in a concentration of 10 to 42 wt. %. In some embodiments the carboxylic acid contains from 2 to 7 carbon atoms.
• the carboxylic acid is selected from the group consisting of citric acid, propionic acid, lactic acid, salicylic acid, benzoic acid, glyceric acid, oxalic acid, tartaric acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and trifluoroacetic acid.
• the carboxylic acid is provided as a mixture of carboxylic acids.
• the composition contains phosphonic acid, a salt thereof, or a mixture of phosphonic acid and a salt thereof in a concentration of 0.5 to 98 wt. %.
• said phosphonic acid, salt thereof or mixture of phosphonic acid and a salt thereof is present in a concentration of 0.5 to 1 wt. %. In some embodiments, said phosphonic acid, salt thereof or mixture of phosphonic acid and a salt thereof is present in a concentration of 10 to 98 wt. %.
• said salt is a salt selected from the group consisting of potassium, sodium or ammonium salt.
• the phosphonic acid prior to addition to the aqueous composition, the phosphonic acid has been at least partly neutralized. In some embodiments, said phosphonic acid has been at least partly neutralized by addition of KOH. In some embodiments, said surfactant is present in a concentration of 0.001 to 10 wt.
• said surfactant is present in a concentration of 1 to 10 wt. %. In some embodiments, said surfactant is present in a concentration of 0.001 to 0.1 wt. %. In some embodiments, said surfactant is an alkyl polyglycoside. In some embodiments, said performic acid source is present in a concentration of 0.25 to 98 wt. %. In some embodiments, said performic acid precursor is present in a concentration of 10 to 98 wt. %. In some embodiments, said performic acid precursor is present in a concentration of 0.25 to 1 wt. %.
• said performic acid source is selected from the group consisting of formic acid, formic acid esters, and formic acid salts.
• said phosphoric acid is present in a concentration of 0.00001 to 98 wt. %. In some embodiments, said phosphoric acid is present in a concentration of 0.00001 to 1 wt. %. In some embodiments, said phosphoric acid is present in a concentration of 10 to 98 wt. %. In some embodiments, said oxidizer is present in a concentration of 0.5 to 70 wt. %. In some embodiments, said oxidizer is present in a concentration of 10 to 70 wt. %.
• said oxidizer is present in a concentration of 0.5 to 1 wt. %.
• said oxidizer is selected from the group consisting of inorganic peroxides, nitrates, halogens and halogen compounds, hypohalite compounds, ozone, oxides, permanganate salts, multi-valent chromium compounds, acids, sulfides and Tollens' reagent.
• the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium percarbonate, sodium periodate, sodium persulfate, ammonium persulfate, sodium perborate, sodium peroxide, calcium peroxide, silver (II) oxide, chlorine dioxide, diacyl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, urea hydrogen peroxide, ammonium hydrogen peroxide, ozone, sodium peroxydisulfate, potassium peroxydisulfate and ammonium peroxydisulfate.
• the composition further comprises performic acid.
• the concentration of said performic acid is from 1 ppb to 50 wt. %. In some embodiments, the concentration of said performic acid is from 5 to 50 wt. %. In some embodiments, the concentration of said performic acid is from 1 ppb to 1000 ppm. In some embodiments, the composition does not contain said oxidizer. In some embodiments, the composition does not contain a performic acid source or performic acid. In some embodiments, the composition contains performic acid and in which the concentration of performic acid therein decreases by not more than 1% over 6 months at a temperature below 20° C. In some embodiments, the concentration of performic acid therein decreases by not more than 1% over 6 months at a temperature of 20° C.
• the composition is such that at a concentration of 20 ppm performic acid and a contact time of one minute at room temperature, the composition achieves a 10000-fold (4 log) reduction in the cfu of a pathogen grown on a designed growth medium, wherein the pathogen is at least one of the pathogens selected from the group consisting of Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), Enterococcus hirae (ATCC 10541), Candida albicans (ATCC 10231), Aspergillus niger (ATCC 16404), Listeria monocytogenes (ATCC 19115) and Penecillium w.t.
• the pathogen is at least one of the pathogens selected from the group consisting of Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas
• the composition is such that at a concentration of 20 ppm performic acid and a contact time of one minute at room temperature, the composition achieves a 100000-fold (5 log) reduction in the cfu of a pathogen grown on a designed growth medium, wherein the pathogen is at least one of the pathogens selected from the group consisting of Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), Enterococcus hirae (ATCC 10541) and Listeria monocytogenes (ATCC 19115).
• Escherichia coli ATCC 8739
• Staphylococcus aureus ATCC 6538
• Pseudomonas aeruginosa ATCC 9027
• Enterococcus hirae ATCC 10541
• Listeria monocytogenes ATCC 19115.
• the composition meets or exceeds at least one of the British Standards BS EN 1276:1997 and BS EN 1276:2009. In some embodiments, the composition exceeds British Standard BS EN 1276:1997. In some embodiments, the composition possesses bactericidal activity within one minute at 20° C. under dirty conditions of 3.0 g/l bovine albumin for at least one of the reference strains E. coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), Listeria monocytogenes (ATCC 19115) and Enterococcus hirae (ATCC 10541).
• the composition possesses bactericidal activity within one minute at 20° C. under dirty conditions of 3.0 g/l bovine albumin for the reference strains E. coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), and Enterococcus hirae (ATCC 10541).
• the composition exceeds at least one of British Standards BS EN 1650:1998 and BS EN 13697:2001.
• the composition possesses fungicidal activity within one minute at 20° C.
• the composition possesses fungicidal activity within one minute at 20° C. under dirty conditions of 3.0 g/l bovine albumin for the reference strains Candida albicans, Aspergillus brasiliensis ( Aspergillus niger ), and Penecilium w.t.
• the composition is substantially free of other microbicides and fungicides.
• a method for making a composition in accordance with embodiments of the invention including a composition according to any one of original claims 61 to 106 , which comprises (a) mixing, not necessarily in the following order, (1) water, (2) at least one of (i) phosphonic acid (HP(O)(OH) 2 ) or a salt thereof and (ii) phosphoric acid, (3) a carboxylic acid, (4) a surfactant, and (b) one of a performic acid source and an oxidizer which can oxidize the performic acid source to performic acid; and (b) thereafter mixing into the mixture the other of the performic acid source and the oxidizer, whereby to generate a composition containing performic acid.
• all of said mixing steps in (a) take place in the liquid phase.
• the mixing in (b) takes place in the liquid phase.
• the oxidizer is ozone and the mixing in (b) takes place in the gas phase.
• the oxidizer is ozone and the mixing in (b) takes place when said ozone is dissolved in water.
• the edible matter has performic acid therein or thereon in an amount of not more than 1 ppm relative to the total amount of edible matter.
• the edible matter on or in which the performic acid and/or silver is present is selected from the group consisting of fruits, vegetables, grains, sprouts, nuts, seeds, meats, meat products, milk, milk products, fish, poultry, eggs, and mixtures thereof.
• the edible matter is selected from the group consisting of apple, avocado, citrus—mandarin, citrus—orange, citrus—mineola, citrus—grapefruit, citrus—lemon, date, kiwi, lychee, mango, peach, pear, persimmon, pomegranate, pepper, asparagus, banana, broccoli, cabbage, carrot, cauliflower, celery, corn, kohlrabi, cucumber, eggplant, garlic, lettuce, onion, peanut, potato, strawberry, sweet pepper, sweet potato, tomato, watermelon, and grape.
• the edible matter is a plant oil that is still in edible form.
• the edible matter is not fully cooked, e.g. the edible matter is uncooked or only partially cooked.
• a method for treating edible matter comprises applying a composition comprising performic acid to the edible matter or a substrate therefor.
• Methods according to various embodiments of the invention may entail treating edible matter at one or more stage(s) in the life-cycle of the edible matter, including, for example, pre-seeding stages, growth, harvest, and post-harvest processing, storage and transport, up through consumption and/or destruction of the edible matter.
• the treating of edible matter may comprise applying the treating composition directly to the edible matter and/or applying the treating composition to substrates for the edible matter, including vessels, such as storage containers (e.g. warehouses, silos, boxcars, sheds, crates).
• substrates for the edible matter including vessels, such as storage containers (e.g. warehouses, silos, boxcars, sheds, crates).
• Such substrates further include, for example, earth, other growth media, and other surfaces or areas, including equipment (e.g., for harvesting, packaging, processing), spaces (e.g., within processing equipment or storage containers), and other surfaces that may come in contact with or in proximity to edible matter.
• performic acid-containing compositions may be used to prevent or inhibit qualitative and/or quantitative losses of edible matter, for example, by applying an effective amount of such a composition to impart increased storage stability or extend shelf life to the edible matter.
• performic acid can decompose to CO 2 after application, and thus, in comparison to fungicides, microbicides and the like that leave residues on crops, soil and in groundwater, is environmentally friendly; consequently, in some embodiments, the performic acid or the performic acid-containing composition is not washed off the thing to which it is applied, e.g. edible matter or a substrate therefor, after its application thereto.
• this decomposition product, CO 2 may function as a nutrient for plants.
• the method may simultaneously treat plants (e.g. to prevent decay or losses by, for instance, disinfecting or killing insects) and provide nutrients thereto, in a single application.
• the method comprises providing CO 2 and/or other nutrients to the edible matter, e.g., growing vegetative matter, for example via decomposition of at least some of the performic acid, or other component, in an amount useful for providing nutrients to the edible matter.
• CO 2 generated by performic acid decomposition may function as an insecticide, acaricide or nematocide or otherwise act to reduce insect, acarid or nematode infestation.
• an increase in the CO 2 concentration in the atmosphere of the storage container such as a silo
• the performic acid may be generated in part using materials, such as potassium bicarbonate, that themselves degrade to release CO 2 .
• Performic acid is often unstable and sometimes even explosive. Accordingly, in accordance with some embodiments, rather than preparing the performic acid composition in advance or transporting it from a manufacturer to the site of use, it can be prepared at or near the site of use, and/or at or near the time of use.
• the performic acid composition can be prepared by, for instance, combining a performic acid source with an oxidizing agent, and this can be done, according to certain embodiments, at or near the site of use, and/or at or near the time of use.
• stable performic acid-containing compositions that exhibit stability for days, weeks or even months
• premixes for forming performic acid that can be transported and mixed on-site with other ingredients to generate performic acid-containing compositions.
• a composition comprising performic acid may be applied in an amount and for a time sufficient to prevent decay of the edible matter.
• “decay” is understood to mean, inclusively, qualitative or quantitative loss. Naturally, the type of loss can depend not only on the type of edible matter, such as plant or meat, but also the life-cycle stage of the edible matter, such as pre-seed, growth, post-harvest or post-slaughter, etc. Some types of decay are not dependent on the stage of life-cycle of the edible matter.
• the decay of certain types of edible matter includes, for example, rotting, blackheart formation, losses from infection with microorganisms or losses from higher organisms, such as insects and rodents. Some types of decay are more prevalent during storage of the edible matter.
• storage includes any stage before or after the edible matter is naturally propagated, such as pre-planting or post-harvest or post-slaughter; as used herein, it also includes periods of storing, for instance in boxes, silos, vessels, etc., transporting, packaging, processing, and distribution.
• decay may be manifested, for example, as decomposing, rotting, sprouting (e.g.
• compositions containing performic acid may be useful as sanitizers, disinfectants and/or sterilizers, and accordingly there are provided methods of sanitizing, disinfecting, and/or sterilizing edible matter or a substrate therefor using a performic acid containing composition.
• the methods may comprise applying one or more performic acid-containing composition(s) that are effective cleaners, antiseptics, sanitizers, disinfectants, and/or sterilizers.
• each of the one or more compositions such as a composition comprising an effective concentration of performic acid, or a performic acid source and an oxidizing agent, can be applied to the edible matter or its substrate in an amount effective to sanitize, disinfect, and/or sterilize the edible matter or substrate(s) therefor.
• such a method may comprise applying one or more compositions, such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, that are effective as nematodecides, miticides, acaricides, fungicides, algaecides, bactericides, virucides, sporicides, anti-yeast agents, and/or an anti-bacteriophages.
• compositions such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, that are effective as nematodecides, miticides, acaricides, fungicides, algaecides, bactericides, virucides, sporicides, anti-yeast agents, and/or an anti-bacteriophages.
• each of the one or more compositions can be applied in an amount effective to destroy, reduce, or control nematodes, mites, ticks, fungi, algae, bacteria, viruses, spores, yeast, and/or bacteriophages when applied to the edible matter or substrate(s) therefor.
• methods of controlling or destroying harmful higher organisms such as insects, rodents and weeds, in or near edible matter or a substrate therefor.
• This may comprise applying one or more formic acid-containing compositions that are effective insecticides, rodenticides, and/or herbicides.
• each of the one or more compositions may be applied in an amount and for a time effective to destroy, reduce, or control insects, rodents, and/or plants, such as weeds, when applied to edible matter or substrates therefor.
• the method comprises applying an amount of one or more compositions, such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, effective as a herbicide.
• a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, effective as a herbicide.
• herbicide activity can be useful to prevent or destroy weeds.
• herbicidal activity is achieved at higher concentrations and application volumes than are necessary or used in treatments of edible matter to kill pathogens and the like.
• the applying comprises applying an amount of one or more of the compositions, such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, effective to control, prevent, inhibit, eliminate or reduce at least one of decomposing, rotting, and black heart formation.
• the applying comprises applying an amount of one or more of the compositions effective to control, prevent, inhibit, eliminate, or reduce sprouting, blossoming, germinating, rooting, or dehydrating of the edible matter.
• the applying comprises applying an amount of one or more of the compositions effective to control, prevent, inhibit, eliminate or reduce infection or disease in the edible matter, for instance at any stage of the life cycle of the edible matter.
• the applying comprises applying an amount of one or more of the compositions effective to control, prevent, inhibit, eliminate or reduce contamination by various pathogens.
• the applying comprises adding an amount of one or more of the compositions, such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, effective to control, prevent, inhibit, eliminate or reduce pathogens, such as seed-borne diseases, soil-borne diseases, water-borne diseases and/or air-borne diseases, and/or insects that act as vectors for and therefor spread such diseases.
• the compositions such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, effective to control, prevent, inhibit, eliminate or reduce pathogens, such as seed-borne diseases, soil-borne diseases, water-borne diseases and/or air-borne diseases, and/or insects that act as vectors for and therefor spread such diseases.
• the performic acid or the composition is applied to edible matter contained in a storage vessel, or to the storage vessel itself, and the edible matter is retained in the storage vessel for a period of at least 1 day, at least 2 days, at least 3 days, at least 4 days, at least 5 days, at least 6 days, at least 7 days, at least one week, at least two weeks, at least three weeks, at least four weeks, at least five weeks, at least six weeks, at least seven weeks, or at least eight weeks after such application.
• the storage vessel is not moved after the perfomic acid is applied to the edible matter therein and/or to the storage vessel itself.
• the storage vessel is an immobile storage vessel.
• the method comprises arresting, reducing or reversing sprouting of edible matter, for instance, sprouting of tubers, such as potatoes or sweet potatoes, for example while in storage, by applying, for example, a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent.
• Arresting sprouting includes stopping or slowing the elongation of sprouts as well as the shortening of the length of sprouts relative to the length of sprouts of untreated tubers.
• the sprouting of tubers may be reversed, such that the total amount or degree of sprouting, such as due to sprouting during storage, is reduced.
• RH relative humidity
• RH relative humidity
• tubers such as potatoes
• roots such as carrots or sweet potatoes
• RH relative humidity
• Storage at high RH can provide the benefit of, for example, preventing weight loss by dehydration during storage, in some instances even for extended periods of time.
• dehydration during storage is one of the major sources of weight loss in potatoes;such weight loss of the stored product translates directly to an economic loss.
• water losses, for example from stored potatoes can make edible matter undesirably soft, or more vulnerable to bruising, pathogenic attack and decay.
• known methods for storing potatoes at high RH generally promote sprouting and rooting, and often favor the growth of undesirable pathogens leading to qualitative and quantitative losses.
• the method comprises storing or maintaining the edible matter at high RH without incurring significant quantitative or qualitative losses.
• the method comprises storing or maintaining the edible matter at high RH without incurring significant quantitative or qualitative losses.
• by treating the edible matter before and/or during storage with a performic acid containing composition it is possible in accordance with some embodiments to store or maintain the edible matter at high RH and, simultaneously, at relatively high temperature, e.g., with a relatively little refrigeration (as opposed to a high degree of refrigeration), without incurring significant quantitative or qualitative losses. This could, for instance, provide significant energy savings over the lower temperature refrigeration that is usually required for storage of edible matter, particularly under conditions of high RH.
• the method comprises applying to the edible matter or its substrate a composition, such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, under conditions of high RH and/or otherwise controlled atmosphere.
• a composition such as a composition comprising an effective concentration of performic acid or a performic acid source and an oxidizing agent, under conditions of high RH and/or otherwise controlled atmosphere.
• the RH may be, for example, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95%.
• the RH can be, for example, from 50% to 100%. For instance, in some embodiments, the RH ranges from 60% to 98%, such as from 70% to 95%.
• the method comprises applying a performic acid containing composition to reduce or control decay at elevated temperatures, e.g., above their typical cold storage conditions.
• onions can be stored at around 0.5° C. to 1° C. to reduce or control decay, but at higher temperatures, such as ambient temperatures, can be treated as described herein to also reduce or control decay without cold storage, or with storage at a higher temperature.
• certain types of table potatoes which otherwise would be stored at 3° C., may be treated as described herein to additionally reduce or control decay at a storage temperature which is not as cold, such as at 7 or 8° C., which is more cost effective and environmentally friendly.
• a method for improving the storage of edible matter comprising contacting the edible matter or a substrate therefor with performic acid, and then storing the edible matter either (a) at low-temperature conditions typically used for the storage of such edible matter, but for a period of time longer than such low-temperature conditions generally facilitate, or (b) for a period of time that is usually facilitated by low-temperature conditions, but at a temperature higher than is typically required for storage of the edible matter for such a period of time.
• application of performic acid contai ning compositions can be used to enhance or strengthen the resistance of a living plant to external forces.
• the method may enhance or strengthen the resistance of a plant to insects, or disease.
• enable or strengthen the resistance of a plant is meant the enhancement or strengthening of resistance of a plant's native or natural ability to maintain its health.
• agents that strengthen a plant's resistance such as salicylic acid or certain essential oils, which can stimulate a plant's immune system, can be used.
• the composition comprises an effective concentration of performic acid or a performic acid source and an oxidizing agent and an agent for increasing such resistance, such as salicylic acid or certain essential oils, such as caraway oil, capsicum oil, citronella oil, clove oil, dill oil, eucalyptus oil, limonene or D-limonene, grapefruit oil, lemon oil, lemongrass oil, lime oil, mint oil, oregano oil, peppermint oil, pine oil, rosemary oil, spearmint oil, and tea tree oil.
• the agent to enhance resistance can, according to certain embodiments, provide additional functions as well.
• salicylic acid can also provide pH regulation to the composition(s).
• the salicylic acid may be combined with an alcohol, which may provide further benefits, e.g. regeneration of performic acid and/or formic acid by reaction with carbon monoxide released when performic acid and/or formic acid decompose.
• the method may enhance or strengthen resistance of a plant to external forces when the plant lacks genetic modification used to enhance or strengthen or strengthen such resistance, i.e., a natural plant.
• the agent to enhance resistance can be applied at any stage during the life cycle of the plant, including to seeds, during growth of the plant, or post-harvest.
• the method also may enhance or strengthen resistance of a genetically-modified plant to external forces, wherein the genetic modification is used to enhance or strengthen such resistance.
• performic acid source is understood to mean any material that can be oxidized to produce performic acid.
• performic acid containing composition will be understood as including both a composition that comprises performic acid, as well as a combination that includes a performic acid source and an oxidizing agent; the latter may be, for example, an aqueous solution containing e.g.
• (1) formic acid and (2) H 2 O 2 and/or O 3 (which will result in formation of performic acid in the solution), or it may be an aqueous composition containing formic acid which when fogged or gassed onto fruits, grains and the like or into enclosed spaces in an ozone-rich atmosphere results in formation of performic acid in such spaces and on surfaces exposed to the fog or gas, including surfaces of fruits, grains and the like as well as the walls of such enclosed spaces, such as storage rooms, silos, hospital rooms, train cabins, airplane cabins, bus interiors or equipment therein, such as hospital equipment.
• Exemplary performic acid sources include formic acid, formic acid esters, and formic acid salts, such as water soluble salts of formic acid, for instance, alkali metal formates, such as sodium formate and calcium formate, formaldehyde, formamide.
• the performic acid source may comprise more than one substance, such as substances that combine to produce formic acid, formic acid esters, formamide, and the like.
• the performic acid source comprises sulfuric acid and sodium formate; carbon monoxide and alcohol; methyl formate and ammonia; and/or formaldehyde and atmospheric oxygen.
• the performic acid source comprises at least one of formic acid, salts of formic acid, and esters of formic acid.
• the performic acid source comprises formic acid as the sole performic acid source or, in other embodiments, as one of multiple performic acid sources.
• the performic acid source may comprise formic acid in an amount ranging from 85% to 100%, by weight, relative to the total weight of the performic acid source, with the remainder being a performic acid source other than formic acid.
• the performic acid source comprises formic acid in an amount ranging from 90% to 100%, by weight, such as from 95% to 100%, or from 99% to 100%, relative to the total weight of the performic acid source.
• the performic acid source consists essentially of formic acid.
• the performic acid source comprises an ester of formic acid.
• Esters of formic acid include, for example, ethyl formate, methyl formate, propyl formate, and mixtures thereof. While useful according to certain embodiments, esters of formic acid have relative disadvantages with respect to, for example, the types of catalysts that can be used, which could affect reaction time and/or yield. Thus, selection of the performic acid source may be based, for example, on considerations of the desired catalyst and, for example, considerations relating to yield, reaction time, reaction robustness or explosivity concerns, the edible matter to be treated, and/or the manner of applying. Thus, in some embodiments, esters of formic acid are not used as the performic acid source, or are used in amounts less than 3%, by weight, such less than 2%, or less than 1%, relative to the total weight of the performic acid source.
• preparing a composition comprising performic acid comprises combining a performic acid source with an oxidizing agent.
• the amount of performic acid source ranges from 1% to 20%, or from 1% to 15%, or 1% to 10%, 1% to 9%, 1% to 8%, 1% to 7%, 1% to 6%, 1% to 5%, 1% to 3%, or 1% to 2% by weight relative to the total weight of the composition in intermediate compositions, such as described in the examples below.
• the performic acid source can be used in much higher concentrations, for instance up to 99% by weight relative to the total weight, in intermediate compositions, such as those discussed herein.
• the amount and type of the performic acid source and the amount and type of the oxidizing agent may be sufficient to produce performic acid.
• amounts and types of the performic acid source and oxidizing agent may be sufficient to produce performic acid in an amount and/or a concentration (e.g. 1 ppb to 40 wt. %) to provide the desired function, e.g., disinfecting, or prevent the decay of the edible matter.
• amounts and types of the performic acid source and oxidizing agent may be sufficient to produce performic acid in an amount of greater than 10 ppm.
• the concentration of performic acid can be measured, for example, by the method disclosed in Lucasr et al., Performic Acid (PFA): Tests on advanced primary effluent shows promising disinfection performance, WST 59.1, p. 89-96 (2009).
• PFA Performic Acid
• the type of performic acid source may be chosen based on compatibility with other components of the composition, such as catalysts.
• the performic acid source in some embodiments, may provide additional functions or characteristics to the composition, such as herbicidal properties, or corrosive properties that may be advantageous, for instance, in treating substrates, foliage or sprouts. For example, at the end of potato growth period, such as after 100 days, potato foliage should be destroyed to prevent further excessive growth, and this result can be achieved, according to certain embodiments, at least where the performic acid source comprises formic acid.
• the performic acid source may, in addition to being a source for performic acid, function to reduce or control weed growth.
• the composition may comprise at least one additive.
• the method comprises combining or using together the least one additive and the performic acid source and the oxidizing agent.
• Combining can be simultaneous or sequential, including adding different components at different times and/or in the same composition or in multiple compositions, which multiple compositions can be combined.
• a composition may be prepared by preparing one or more intermediate compositions.
• any additive useful in compositions relating to treating edible matter or its substrates may be used.
• the additive may be at least one of a disinfectant, surfactant, antifoaming agent, anti corrosion agent, coloring agent, odorant, lubricant, essential oil, emulsifier, homogenizer, chelating agent, stabilizer, synergist, viscosity regulator, pH regulator, solvent, promoter, modifier, trace element activator, inorganic or organic additive, corrosion inhibitor, or flavoring agent.
• one additive may have more than one function or provide more than one property.
• a composition can comprise a pH regulator.
• a pH regulator may be used, for example, to control or stabilize the oxidizing of the performic acid source by the oxidizing agent.
• a pH regulator may be used, as another example, to provide additional functions, such as disinfecting.
• a pH regulator may be used, as yet a further example, to effect the pH of the composition when applied to the edible matter or its substrate, for instance so as to avoid or diminish any unwanted damage to or reaction with the edible matter or its substrate.
• the pH regulator may comprise, for example, at least one second acid, at least one base, and/or at least one pH buffer. Suitable pH regulators may be selected based on, for example, compatibility with other ingredients in the composition, the material to which the composition is to be applied, and/or the method of application, e.g., the application equipment.
• the pH regulator may comprise at least one second acid.
• second acid is understood to mean an acid that is not performic acid or the performic acid source, regardless of whether or not the performic acid source is or is not an acid and regardless of whether or not the performic acid or the performic acid source affects the pH of the composition.
• second acid is used for definitional purposes and is not intended to imply that the composition necessarily comprises a first acid. Further, as discussed herein, the second acid may or may not be used to provide pH regulation.
• suitable second acids may be selected based on, for example, compatibility with other ingredients in the composition, the material to which the composition is to be applied, and/or the method of application.
• the type and concentration of the second acid may be chosen based on its function in providing pH control, such as pH control depending on the other components and/or in view of the length of time between composition preparation and application, the type of edible matter or substrate, toxicity, the life-cycle stage, intended storage time or conditions, other components in the composition, and/or the manner of application, such as fogging or dipping, the duration of application, ambient conditions during application, etc.
• the type and concentration of a second acid may be chosen to provide additional function for treating edible matter or its substrate, such as disinfecting.
• the at least one second acid may be selected from mineral acids, sulfonic acids, carboxylic acids, vinylogous carboxylic acids, and nucleic acids, organic acids and inorganic acids, and may be monoprotic or polyprotic, or strong or weak.
• Exemplary second acids that may be used include, but are not limited to, phosphonic, phosphoric, sulfuric, nitric, oxalic, citric, tartaric, boric, bromic, stannic, peracetic, hydrochloric, salicylic, and sulfuric acid, hydrofluoric, hydrobromic, acetic, chloroacetic, dichloroacetic, trichloroacetic, trifluoroacetic, benzoic, lactic, uric, fluorosulfuric, hypochloric, chloric, perchloric, periodic, fluorosulfuric, fluoroantimoic, fluoroboric, chromic, methanesulfonic, ethanesulfonic, benzenesulfonic, ascorbic, deoxyribonucleic, ribonucleic, hydroiodic, and p-Toulenesulfonic acid.
• the second acid is or comprises a carboxylic acid.
• the second acid is selected from hydrochloric, phosphonic, phosphoric, sulfuric, nitric, oxalic, citric, tartaric, boric, bromic, stannic, peracetic, hydrochloric, salicylic, and sulfuric acid.
• at least one second acid is phosphonic acid.
• the second acid is present in the final or an intermediate composition in a concentration ranging from 10 ppm to 90% by weight relative to the total weight of the composition.
• the second acid may be present in an amount ranging from 10 ppm to 70%, or from 10 ppm to 50%, such as from 10 ppm to 20%, or from 10 ppm to 10%, or from 10 ppm to 5%, or from 10 ppm to 1%, by weight relative to the total weight of the final or intermediate composition.
• the pH regulator may comprise at least one base.
• the type and concentration of base may be selected to be, for example, compatible with other ingredients in the composition, based on the material to which the composition is to be applied, and/or the method of application, e.g., the application equipment.
• the base may be chosen to provide pH control, such as pH control depending on the other components and/or in view of the length of time between composition preparation and application, the type of edible matter or substrate, the life-cycle stage of the edible matter, intended storage time or conditions, and/or the manner of application, such as fogging or dipping, the duration of application, ambient conditions during application, etc.
• the base may be chosen to provide additional function for treating edible matter or its substrate, such as disinfecting.
• the at least one base may be selected from hydroxides, such as lithium hydroxide, sodium hydroxide (caustic soda or lye), potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide; caustic soda, ureas, carbonates, ammonia, alanine, amines, such as dimethylamine, ethylamine, glycine, hydrazine, methylamine, trimethylamine, pyridine, or ammonium hydroxide.
• the at least one base is chosen from caustic soda, ammonia, and urea.
• the pH regulator comprises one or more buffers.
• the type and concentration of buffer and buffer components may be selected to be, for example, compatible with other ingredients in the composition, based on the material to which the composition is to be applied, and/or the method of application, e.g., the application equipment.
• the buffer may comprise one or more of citric acid buffers, glycine buffers, acetic acid buffers, cacodylic acid buffers, bicarbonate buffers, pipes buffers, tris buffers, imidazole buffers, phosphate buffers, triethanolamine buffers, taps buffers, boric acid buffers, and piperidine buffers.
• the buffer may comprise hydrochloric acid and potassium chloride; glycine and hydrochloric acid; potassium hydrogen phthalate and hydrochloric acid; citric acid and sodium citrate; sodium acetate and acetic acid; potassium hydrogen phthalate and sodium hydroxide; disodium hydrogen phthalate and sodium dihydrogen orthophosphate; dipotassium hydrogen phthalate and potassium dihydrogen orthophosphate; barbitone sodium and hydrochloric acid; sodium tetraborate and hydrochloric acid; glycine and sodium hydroxide; sodium tetraborate and sodium hydroxide; sodium hydrogen orhotphosphate and sodium hydroxide; potassium chloride and sodium hydroxide; or mixtures thereof.
• the pH regulator adjusts the pH of the composition to a pH ranging from 0.1 to 8.
• the second acid can adjust the pH of the composition to a pH ranging from 0.1 to 7, or in some embodiments, to a pH ranging from 0.1 to 6, or from 0.1 to 5, or from 0.1 to 3, or from 0.1 to 2, or from 0.1 to 1.
• a pH of from 0.1 to 3 has been found particularly useful to stabilize the composition without causing substantial losses of the edible matter treated.
• the at least one additive comprises at least one essential oil.
• the type and concentration of essential oil may be selected based on, for example, the desired properties of the essential oil, toxicity of the essential oil, compatibility with other ingredients in the composition, based on the material to which the composition is to be applied, and/or the method of application, e.g., the application equipment.
• Essential oils are generally volatile, liquid aroma compounds derived from natural sources, such as from plants, and are typically, but not always, poorly soluble in water.
• the type and concentration of essential oil may be used, for example, to provide enhanced or additional characteristics to the composition, such as anti-microbial, antiseptic, antiviral, herbicidal or insecticidal properties, fragrance, scent, medicinal characteristics, physical properties (e.g., viscosity) and/or flavor.
• Exemplary essential oils include, but are not limited to, agar oil, allspice essential oil, ajwain oil, angelica root oil, anise oil, asafoetida, balsam oil, basil oil, bay, benzoin oil, bergamot oil, boldo oil, black pepper oil, buchu oil, birch oil, bitter almond oil, cajuput oil, calamus oil, camphor, cannabis flower oil, caraway oil, cardamom seed oil, carrot seed oil, cassia oil, catnip oil, cedarwood oil, chamomile oil, calamus root, cinnamon oil, cistus, citronella oil, clary sage oil, clove leaf oil, coffee, coriander, costmary oil, costus root, cranberry seed oil, cubeb, cumin oil, cypress oil, cypriol, curry leaf, davana oil, dill oil, eleni oil, elecampane, eucalypt
• the essential oil is chosen from at least one of caraway oil, citronella oil, clove oil, dill oil, eucalyptus oil, limonene or D-limonene, grapefruit oil, lemon oil, lemongrass oil, lime oil, mint oil, oregano oil, peppermint oil, pine oil, rosemary oil, spearmint oil, and tea tree oil.
• compositions can, in some embodiments, comprise stabilizers and/or viscosity modifiers.
• the type and concentration of stabilizers and/or viscosity modifiers may be selected based on, for example, compatibility with other ingredients in the composition, the material to which the composition is to be applied, and/or the method of application, e.g., the application equipment.
• Exemplary stabilizers and modifiers include, but are not limited to, citric acid, tartaric acid, boric acid, bromic acid, stannates, phosphonic acids, glycerin and silicone.
• a stabilizer and/or viscosity modifier can be used, for example, to slow down the decomposition of the formula.
• a stabilizer may slow the reaction or decomposition of aperoxide and/or prolong the life of an oxidizing agent either before or after adding the composition to the edible matter.
• the amount and type of a stabilizer and/or modifier may be based on, for example the desired degree of stabilization or viscosity modification, the other components of the composition, the manner of applying, toxicity, and other desired characteristics.
• the stabilizer comprises phosphoric acid. In some embodiments, the stabilizer comprises phosphates, such as disodium phosphate (such as Dequest® 2010).
• the stabilizer and/or viscosity modifier may provide additional functions or benefits.
• phosphonic acid and/or phosphoric acid and/or some essential oils can stabilize an oxidant and can also be, in some embodiments, a disinfectant.
• compositions can optionally comprise one or more trace element activators to active the oxidizer; materials that act synergistically with the performic acid, performic acid source, oxidizer and/or other ingredients in the composition to provide improved efficacy; and/or promoters.
• Trace element activators, synergists and/or promoters can be used, for example, to increase or influence the initiation or rate or extent of a reaction, for instance, by influencing or initiating a reaction themselves or by activating a catalyst.
• Trace element activators, synergists and promoters include, but are not limited to, metals (e.g.
• suitable trace element activators, synergists and promoters may include one or more of titanium, copper, zinc, nickel, iron, potassium, manganese, silver, chromium, molybdenum, and magnesium.
• Other activators may be boron, phosphorus, iodine, sulfur, citrate, or oxides thereof or salts thereof.
• the amount and type of the trace element activator(s), synergist(s) and/or promoter(s) may be based on, for example, the desired degree of activation, synergism and/or promotion, the other components of the composition, the type of edible matter, residues, toxicity, and manner of applying, and the like.
• the synergist and/or promoter comprise sulfuric acid.
• the synergist and/or promoter can provide additional functions or benefits.
• sulfuric acid can enhance performic acid production, and can also be, in some embodiments, a disinfectant and/or a pH regulator and/or a herbicide and/or a source of internal heat, for instance when heat is used to catalyze the oxidation.
• compositions can, in some embodiments, comprise at least one inorganic or organic additive.
• organic or inorganic additives may include, in addition to the aforementioned additives, peracetic acid, phenol, gelatin, glycerin, sodium azide, polymoxin B, sodium bicarbonate, pectin, salicylic acid, alcohols, ionic and nonionic adjuvants, surfactants, silicones, phosphates, phosphonates, etidronic acid (HEDP), and essential oils.
• Inorganic or organic additive can be used, for example, to enhance efficacy of the treatments.
• the types and amount of inorganic the desired degree of activation, synergism and/or promotion, the other components of the composition, the type of edible matter, residues, toxicity, and manner of applying.
• the composition comprises glycerin.
• Glycerin can be used, for example, to regulate viscosity, or may be used as a wetting agent, for instance to prolong the stability of the composition on the surface of the treated edible matter.
• glycerin may slow or delay the evaporation of the composition from or near the surface or within the edible matter, increasing the contact time of the composition with the edible matter or the substrate, such as soil.
• the composition may comprise glycerin in an amount ranging from 0% to 10%, by weight relative to the total weight of the composition, such as 0%, not more than 0.001%, not more than 0.01%, not more than 0.1%, not more than 1%, not more than 2%, not more than 3%, or from 0.1% to 9%, or from 0.1% to 8%, or from 0.1% to 7%, or from 0.1% to 6%, or from 0.1% to 5%, or from 0.1% to 4%, by weight relative to the total weight of the composition.
• the additive comprises one or more surfactants.
• Surfactants may lower the surface tension of the composition. Accordingly, the selection of surfactant may depend on the properties and components of the composition, the desired viscosity, the manner of application, toxicity, cost, and other properties of the surfactant. For example, the surfactant may provide other characteristics, functions, or properties to a composition, such as disinfectant properties. Suitable surfactants may be found among the cationic, anionic, non-ionic and amphoteric surfactants.
• the composition further comprises at least one solvent.
• the type and amount of solvent may be chosen, for example, based on the desired properties of the solvent, compatibility with other ingredients of the composition, the method of application, toxicity and environmental considerations, and the like.
• the solvent comprises at least one alcohol, such as acetic alcohol, methanol, and/or ethanol.
• the additive may comprise one or more antifoaming agents, such as silicon or glycerin; corrosion inhibitor or anticorrosion agents, such as silicons or phosphates; coloring agents; odorants, such as essential oils; lubricants, such as gelatin or glycerin or silicone; emulsifiers, such as alcohols; homogenizers, such as alcohols, gelatin, glycerin, or sodium azide; chelating agents, such as phosphates, HEDP, or phosphonates; viscosity regulators, such as gelatin, glycerin, or pectin; flavoring agents, such as essential oils; and/or disinfectants, such as peracetic acid, sodium azide, salicylic acid, polymoxin B, or phenol; amphoteric agents, such as sodium bicarbonate.
• antifoaming agents such as silicon or glycerin
• corrosion inhibitor or anticorrosion agents such as silicons or phosphates
• coloring agents such as odorants, such
• the amount and type of additive may be based on, for example, the other components of the composition, the type of edible matter, the residue of the additive, toxicity, manner of applying, environmental or regulatory considerations, etc. As discussed elsewhere in the application, some compounds may belong to one or more than one of these categories, and may have functions or properties other than the aforementioned.
• the pH of the composition comprising performic acid ranges from 0.1 to 8.
• the pH of the composition may range from 0.1 to 7, or from 0.1 to 6, or from 0.1 to 5, or from 0.1 to 3, or from 0.1 to 2, or from 0.1 to 1.
• the pH of the composition may be controlled, according to certain embodiments, in order to, for example, do one or more of control or stabilize the oxidizing of the performic acid source by the oxidizing agent, provide additional functions, or avoid or diminish any unwanted damage to or reaction with the edible matter.
• the composition comprises or is formed using at least one oxidizing agent.
• the oxidizing agent can be any oxidizer compatible with the performic acid composition, for example capable of oxidizing the performic acid source to performic acid. Oxidizing agents are known in the art, and the type and concentration can be selected based on, for example, compatibility with various components, safety profile, and applicability under certain conditions (e.g, pH, temperature) and based on the present disclosure. The choice of oxidizing agent may depend on various factors, relating to the robustness of the oxidation required, the manner or mode of applying the edible matter, or the nature of the edible matter and intended applications.
• H 2 O 2 and O 3 may be desirable as oxidizing agents in applications wherein the edible matter or its substrate is a food for human consumption, or soil for growing food sources for human consumption, etc.
• the oxidizing agent is biodegradable, that is it will decompose by natural processes and chemical processes within the system into more basic components, for instance components containing carbon, hydrogen, and oxygen (water, carbon dioxide, and the like).
• hydrogen peroxide is generally biodegradable.
• the oxidizing agent may provide one or more additional functions, such as disinfecting.
• Oxidizing agents include, but are not limited to, inorganic peroxides, nitrates, halogens and halogen compounds, hypohalite compounds, ozone, oxides, permanganate salts, multi-valent chromium compounds, acids, sulfides or Tollens' reagent.
• the oxidizing agent is selected from hydrogen peroxide, sodium percarbonate, sodium periodate, sodium persulfate, ammonium persulfate, sodium perborate, sodium peroxide, calcium peroxide, silver (II) oxide, chlorine dioxide, diacyl peroxides, such as benzoyl peroxide, ketone peroxides, such as ((2,4-pentanedione peroxide), peroxydicarbonates, such as diisopropyl peroxydicarbonate, peroxyesters, dialkyl peroxides, hydroperoxides, such as t-butyl hydroperoxide, peroxyketals, such as 2,2-di(t-butyl peroxy)butane, urea hydrogen peroxide, ammonium hydrogen peroxide or ozone.
• diacyl peroxides such as benzoyl peroxide
• ketone peroxides such as ((2,4-pentanedione peroxide)
• the oxidizing agent comprises one or more of sodium, potassium and ammonium peroxydisulfates. In at least one embodiment, the oxidizing agent comprises at least one of hydrogen peroxide, urea hydrogen peroxide, ammonium hydrogen peroxide, or ozone. According to certain embodiments, the oxidizing agent further comprises water.
• the composition comprises hydrogen peroxide.
• the hydrogen peroxide may be used in an concentration ranging from 10 ppm to 60%, by weight relative to the total weight of the composition, for example from 1% to 60%, or from 1% to 50%, or from 1% to 40%, or from 1% to 30%, or from 1% to 20%, or from 1% to 10%, or from 5% to 10%, such as from 6% to 10%, by weight relative to the total weight of the composition.
• Oxidation of performic acid source to performic acid can be catalyzed or non-catalyzed.
• the oxidation of the performic acid source can be catalyzed.
• the catalyzing comprises at least one of controlling the ratio of the perfomic acid source to the oxidizing agent in the composition, heating the composition, adjusting the pH of the composition, adding at least one catalyst to the composition, and/or irradiating the composition.
• the catalyzing may comprise controlling the ratio of the performic acid source to the oxidizing agent in the composition to be from 1:1000 to 1000:1 by volume, heating the composition, adjusting the pH of the composition to be from 0.1 to 8, adding at least one catalyst to the composition, or irradiating the composition.
• the catalyzing comprises controlling the ratio of the performic acid source to the oxidizing agent in the composition.
• the ratio of the performic acid source to the oxidizing agent in the composition may range from 1:1000 to 1:1000.
• the ratio may range from 1:500 to 500:1, or from 1:200 to 200:1, or from 1:100 to 100:1, or from 1:50 to 50:1, or from 1:20 to 20:1, or from 1:10 to 10:1, such as from 1:8 to 8:1, or from 1:7 to 7:1, or from 1:6 to 6:1, or from 1:5 to 5:1, or from 1:4 to 4:1, or from 1:3 to 3:1, or from 1:2 to 2:1, or the ratio may be 1:1 on a molar basis.
• the ratio of performic acid source to oxidizing agent is at least 1000:1, is not more than 1000:1, is not more than 500:1, is not more than 200:1, is not more than 100:1, is not more than 50:1, is not more than 20:1, is not more than 10:1, is not more than 8:1, is not more than 7:1, is not more than 6:1, is not more than 5:1, is not more than 4:1, is not more than 3:1, is not more than 2:1, or is not more than 1:1 on a molar basis.
• the catalyzing comprises adjusting the pH of the composition, for example adjusting the pH of the composition to be from 0.1 to 8. In at least one embodiment, the catalyzing comprises adjusting the pH of the composition to be from 0.1 to 7, or from 0.1 to 5. In some embodiments the catalyzing comprises adjusting the pH of the composition to be from 0.1 to 3.
• the catalyzing comprises adding at least one catalyst to the composition.
• the catalyst may comprise at least one of metal ions, acids, bases, or esters.
• the type and amount of catalyst can be chosen based on, for example, compatibility with other ingredients in the composition, the type and amount of residues, cost, the amount of energy or heat that would be generated in the reaction, and/or the degree of catalysis desired and additional functionalities.
• the catalyst may comprise at least one of metal, for instance a transition metal, such as, but not limited to, metal ions or metals from any of groups III to XII of the periodic table, and/or including transition metals, salts thereof and/or derivatives thereof, and/or metal oxides.
• a transition metal such as, but not limited to, metal ions or metals from any of groups III to XII of the periodic table, and/or including transition metals, salts thereof and/or derivatives thereof, and/or metal oxides.
• the catalyst may be a metal ion, such as, but not limited to copper, zinc, nickel, iron, titanium, chromium, manganese, or silver.
• the catalyst may comprise acids, such as nitric acid; esters, or any other catalyst known in the art, for example, potassium, potassium permanganate, chromium, molybdenum, titanium and compounds or ions of phosphorous, iodine, sulfur, citrate, or ions or fine particles of lithium.
• acids such as nitric acid; esters, or any other catalyst known in the art, for example, potassium, potassium permanganate, chromium, molybdenum, titanium and compounds or ions of phosphorous, iodine, sulfur, citrate, or ions or fine particles of lithium.
• the catalyst is a metal.
• the metal can be chosen from elements of groups III to XII of the periodic table, and/or can comprise metal ion(s).
• the metal is chosen from copper, zinc, nickel, iron, manganese, titanium, and silver ions.
• the catalyst comprises silver ions.
• the metal ions may be present in the composition in a concentration ranging from 1 ppb to 5 wt. %.
• the metal ions are present in a concentration ranging from 1 ppb to 2 wt. %, or from 1 ppm to 2 wt. %, or from 1 ppm to 1 wt. %, or from 1 ppm to 1000 ppm, or from 1 ppm to 100 ppm, or from 1 ppm to 50 ppm, or from 1 ppm to 10 ppm.
• the concentration of metal or metal ions can, for example, be chosen based on, e.g., degree of catalysis desired and/or suitability for the type of edible matter or substrate therefor, toxicity, environmental and other regulations and considerations, cost, other functions and/or the manner of application, and the like.
• the metal in addition to its function as a catalyst, may provide enhanced or additional characteristics to the composition, such as disinfectant properties, including synergistic disinfectant properties when combined with an oxidant, bacteriostatic properties, and/or antimicrobial properties.
• the catalyzing comprises irradiating the composition.
• Irradiating the composition includes applying radiation from a natural source, such as the sun, or non-natural radiation source, such as UV or IR lamp.
• the composition may be subjected to radiation, such as Ultraviolet (UV), infrared (IR) radiation, or visible radiation.
• UV radiation is chosen from UV and IR radiation.
• the radiation is both UV and IR radiation.
• UV radiation is radiation having a wavelength of less than 400 nm and IR radiation has a wavelength of greater than 700 nm.
• Such radiation can be applied to the composition before or after treating the edible matter or substrate therefor and in any manner known to those of skill in the art. If UV and IR radiation are applied to a composition, they can be applied sequentially or at the same time and in any order.
• IR radiation having a wavelength ranging from 0.75 to 3.0 micrometers is applied to the composition. In further embodiments IR radiation having a wavelength of from 0.75 to 1.4 micrometers is applied. In another embodiment, a wavelength of from 1.4 to 3.0 micrometers is applied.
• UV radiation having a wavelength of less than 300 nm, such as less than 280 nm, or for example, less than 200 nm is applied to the composition. In at least one embodiment, the wavelength ranges from 200 nm to 10 nm.
• the temperature of the composition when applied to the edible matter is at or below room temperature. In other embodiments, the composition when applied to the edible matter is above room temperature.
• the temperature of the composition is elevated before or after applying the composition to edible matter or a substrate therefor.
• the compositions can be effective over a wide range of temperatures.
• the composition remains stable at relatively high temperatures.
• a “stable” composition is a composition that has concentrations or amounts of active ingredients remaining, for example that have not undergone decay, sufficient to control, prevent or reduce qualitative losses, or to perform one or more of the functions described herein.
• the composition is effective in the range of temperatures from 0° C. to 95° C.
• the composition is effective in the range of temperatures from 20° C. to 95° C., such as from 35° C. to 95° C., or for instance from 35° C. to 95° C.
• the stability of the composition can vary depending on the type and/or concentration of the performic acid source and/or oxidant in the composition, the temperature, other components in the composition or exposed to the composition, for example via the edible matter.
• the catalyzing comprises heating the composition.
• the composition can be heated in any manner suitable for heating the composition.
• the composition may be heated by adding external radiant heat, applying the composition to heated edible matter, by applying a second heated composition to the composition, or by chemical reaction, such as supplying heat in the composition via an exothermic reaction.
• a method further comprises applying to the edible matter a second composition.
• the second composition may have a temperature that is different, such as warmer, than the composition discussed hitherto, which in this paragraph and the next paragraph following will be referred to as the first composition.
• the temperature of the second composition is at least 10° C. greater than the temperature of the first composition. In at least one embodiment, the temperature is at least 20° C. greater than the temperature of the first composition.
• the second composition may provide other functions, for instance any of the functions disclosed herein, such as having disinfectant, herbicidal, insecticidal properties, etc. Accordingly, the components of the second composition will depend on the desired function and other considerations such as previously described for instance, toxicity, cost, environmental considerations, and the components in the first composition and/or the second composition and the type of edible matter or substrate.
• the second composition is substantially free of performic acid.
• the second composition may comprise any additive, oxidizing agent, or catalyst, such as those previously disclosed.
• the second composition comprises an oxidizing agent, such as hydrogen peroxide.
• the second composition comprises at least one second acid.
• the performic acid- or performic acid source-containing composition can be applied to the edible matter by any method suitable for applying the given composition to the edible matter or substrate therefor.
• the composition may be applied by spraying the composition on or near the edible matter, such as by hand spraying; by gassing the edible matter with the composition, such as by fogging, for instance dry fogging; by submerging, or dipping, the edible matter in the composition; or by injecting the composition into the edible matter.
• the components of the composition may be applied as dry powders, liquids, gases, or any other readily available form.
• salicylic acid and/or hydrogen peroxide formulations may be applied to the edible matter or substrate in the form of a liquid, an aqueous solution or a dry solid, such as a powder.
• Edible matter and substrates therefor can be treated, according to certain embodiments, by providing the composition via irrigation water.
• the irrigation water can serve as a vehicle for providing the composition to the edible matter or substrate.
• the composition is applied to edible matter or substrates therefor by fogging, such as dry fogging, or by providing a fine spray.
• fogging means spraying droplets with particle sizes of less than and up to 1000 microns in diameter.
• a dry fog may be produced by atomizing systems.
• the composition is applied to the edible matter by dry fogging, wherein the dry fogging comprises applying the composition in the form of droplets of sizes less than or equal to 1000 microns onto the edible matter, such as less than 800 microns in diameter, or less than 100 microns, for instance, less than 10 microns, for example down to 0.001 microns.
• a spray or fog can be formed by any suitable method based on the composition, edible matter or substrate, and/or the site conditions, physical constraints and so forth.
• a spray or fog may be formed by an ultrasonic sprayer or an ultrasonic microdroplet generator, for instance in an electronic method or a method wherein a vibrating disc creates resonance in a liquid, air-liquid sprayers, electric-ultrasonic foggers, cold foggers, hot foggers and the like.
• a dry fog optionally may be characterized by the air-to-liquid volume ratio.
• the methods comprise applying a dry fog formed with an air liquid fogger, and in further embodiments, the fog has an air-to-liquid volume ratio ranging from 300:1 to 1200:1, for instance from 400:1 to 1000:1, or from 500:1 to 900:1, or from 500:1 to 800:1, or from 500:1 to 700:1.
• composition may be applied to edible matter or edible matter substrates intermittently, continuously, or in a single application.
• the optimal concentrations and manner of applying can be determined, for example, based on the manner of applying the composition.
• the composition may be diluted prior to application to prevent adverse deterioration or decay of the edible matter or substrate therefor as a result of the concentrations of components in the composition.
• edible matter includes, for example, foods, meat, plants, flowers, fruits, vegetables, tubers, bulbs, dairy products, grains, seeds, foliage, and drinking water.
• Edible matter is not limited by life-cycle stage, and thus includes for example seeds, bulbs, tubers, meats, plants, vegetables, flowers, foliage, fruits, grains, milk, dairy products, eggs and poultry, at all stages pre-planting or pre-conception through post-harvest or animal maturity, through sales, distribution, and consumption.
• the edible matter is one of meat, plants, flowers, fruits, vegetables, tubers, bulbs, dairy products, and grains.
• the edible matter is seeds.
• edible matter includes cabbage, broccoli, cauliflower, kiwi, pear, pomegranate, eggplant, pepper, melon, carrot, tomato, garlic, persimmon, turnips, eggs, meat and/or animal carcasses, eggs and/or egg shells, milk, cheese, potatoes, sweet potatoes, citrus fruits, such as oranges, tangerines, grapefruits, onions and/or onion bulbs, flower bulbs, and the like.
• edible matter substrates include any substrate or vessel that may contact or be in proximity to the edible matter in the course of the life cycle of the edible matter, from pre-planting to post-harvest, through consumption and/or disposal of the edible matter.
• edible matter substrates include substrates, vessels, and materials used for storage and/or transport, such as boxes, crates, silos, box cars, vehicles; growth media, such as soil, soil substitutes, such as gels, coconut fibers, vermiculite, perlite; and processing facilities.
• the substrate is a growth medium.
• Growth media may be suitable depending on the edible matter, including any materials that can grow or propagate a plant. Growth media can be natural or synthetic. According to certain embodiments, the growth medium is in solid form. Growth media include, for example, soil; vermiculite; perlite; clays, calcined clays, and clay pellets; coconut fibers, cocopeat, coir and coir peat; sand; diatomite; peat and peat-like mosses, such as hypnaceous moss, reed and sedge, humus or muck, and sphagnum moss; wood residues, such as leaf mold, saw dust, and barks; rice hulls; oasis cubes; bagasse; expanded polystyrene; urea formaldehydes; fiberglass; rockwool; gravel; lava rock; polymeric soil substitutes; soil amendments, such as nutrients for the soil, including for example substances comprising phosphoric acid and/
• the substrate is a storage container, such as for meat, plants, flowers, fruits, vegetables, tubers, bulbs, dairy products, grains, or soil.
• Another aspect of the invention is a method of treating edible matter comprising obtaining a composition comprising performic acid in a concentration of at least 10 ppm, and applying the composition to the edible matter or a substrate therefor.
• the method comprises obtaining a composition comprising performic acid in a concentration ranging from 10 ppm to 85 wt. %, relative to the total weight of the composition, and applying the composition to the edible matter or a substrate therefor.
• the composition may comprise performic acid in an amount ranging from 10 ppm to 50 wt. %, or from 10 ppm to 30 wt. %, or from 10 ppm to 20 wt. %, or from 10 ppm to 15 wt. %, or from 10 ppm to 13 wt. %, or from 10 ppm to 10 wt. %, or from 10 ppm to 7 wt.
• the concentration of performic acid may depend on the concentration and types of oxidizing agents, catalysts in the composition, and the like, as well as the conditions for combining as disclosed above.
• the composition comprising performic acid further comprises at least one of oxidizing agents, catalysts, and additives.
• the composition further comprises at least one oxidizing agent, such as those exemplary oxidizing agents disclosed herein.
• the composition further comprises at least one catalyst, such as those exemplary catalysts disclosed herein.
• the composition further comprises at least one additive, such as those exemplary additives disclosed herein.
• composition comprising performic acid may be in any form, such as a spray, a fog, a liquid, or a gas.
• the composition comprising performic acid is a gas, wherein the gas further comprises ozone.
• compositions comprise formic acid and performic acid and at least one additive.
• the additive can comprise any of the components disclosed above, or in the examples below, and may be chosen, for example, based on the desired function, components of the composition, type of edible matter or substrate, manner of applying, and the like.
• the compositions comprising formic acid and performic acid further comprise at least one of an oxidizing agent, a catalyst and an additive.
• the compositions can comprise at least one metal ion.
• the at least one metal ion is at least one of a molybdenum ion, a chromium ion, a copper ion, a zinc ion, a nickel ion, an iron ion, a manganese ion, and a silver ion.
• the composition comprises a silver ion.
• the treatment may be achieved by manipulating either the time of treatment or the time of incubating the composition before applying the composition to the edible matter or to a substrate for edible matter.
• the conditions of such optimization may be selected based on, for example the type of edible matter or substrate, the composition, and/or the manner of applying.
• bactericidal or fungicidal composition that has essentially no gaps in its activity, i.e. it is a wide-spectrum anti-bacterial, anti-fungal, anti-microbial or the like with activity against nearly all strains of bacteria, fungi etc.
• compositions described in the following Examples 1-2 were prepared in the following manner; where multiple ranges or multiple values are listed for a given component, corresponding component amounts were used or contemplated for use over the course of the trial.
• Oxidizing agents were mixed in a first composition with any stabilizers, metal ions, or chelators.
• acids were mixed with deionized water, and the pH was elevated to the target level with one or more bases.
• any solid/powder ingredients were dissolved to liquid stages. Finally, all the above compositions were slowly mixed to create a mixture comprising all the ingredients except the performic acid source.
• the performic acid source was added to the mixture on-site, to generate the compositions comprising performic acid.
• the performic acid in the compositions was not stable, and the compositions were not active, for extended periods of time. That is, the performic acid concentration is not constant, as performic acid tends to decay to yield CO 2 .
• the compositions comprising performic acid were applied to the edible matter within 1-2 hours after combining performic acid with the mixture; application of the compositions under these conditions was also done immediately after mixing.
• the composition comprising performic acid was more stable, and was applied from 5 hours to up to two months after combining the performic acid source with the mixture.
• compositions comprising performic acid on spore production of the silver scurf causal agent, Helminthosporium solani, on infected potato tubers was investigated.
• Silver scurf is widely considered to be a major source of quality loss in the fresh potato market.
• the four treatments for the study were: 1) 30 tubers were hand sprayed once with a 19:1 solution of tap water : performic acid composition (H 2 O 2 7 wt. %, 2 wt. % phosphonic acid, 1 wt. % phosphoric acid, HEDP (etidronic acid) 0.5 wt. %, glycerin 0.5 wt. %, silver 100 ppm, formic acid 3 wt.
• Fogs were generated using ultrasonic foggers (compressed air combined with liquid, or electric ultrasonic foggers).
• the fogs were applied to potatoes at ratios of 200 cc to 1,000 cc per ton of potatoes at a holding temperature of from 7 to 9° C. at time periods of once per month to once every two weeks.
• Sprays were applied to potatoes at a volume of from 2 to 10 L per ton of potatoes with from 0.1% to 2% surfactant.
• Hand sprayed tubers were laid out on a tarp in a single layer and the test solution or water was misted onto the tubers until glistening. The tubers were allowed to dry for 5 minutes, turned over, and the other half was sprayed until glistening. Tubers were allowed to dry for an additional 15 minutes and then placed into plastic mesh bags. Hand sprayed tubers were hung in a storage container and kept at 7.5 C and 92% room humidity (RH). The fogged tubers were placed in the same container. During each fog treatment in the container, the hand sprayed tubers were removed and kept in the dark at room temperature. The hand sprayed tubers where then returned to the container after all the fog had been exhausted from the container. Tubers treated with the fog were treated approximately nine times.
• tubers were washed and placed in plastic potato bags with holes. These bags were placed in potato boxes and incubated at 20° C. at 95% room humidity for 3 weeks. This temperature and humidity treatment is used to induce conidia production in H. solani. After incubation, the area of the tubers surface covered with H. solani spores was estimated by inspecting the tubers with a dissecting microscope. The results are summarized in Table 2 below.
• compositions not comprising performic acid were applied to tubers (composition A), with tubers stored in a separate storage locker serving as an additional control. After several months, compositions comprising performic acid (composition B) were applied to the potatoes. The applied compositions were as described in Table 3.
• Composition A Hydrogen peroxide 7% 5% to 10% Phosphonic acid 3% 1% to 5% HEDP (HP stabilizer) 1% 0.5% to 2% Silver 50 ppm 0, 50, 100, 250 or 500 ppm Benzoic Acid 0 0.1% Surfactant 0 0% to 2% Sulfuric Acid 0.5% to 2% Stabilizer (Solvay) about 1% Glycerin 0.5% to 5% Pure Formic Acid 0 1% to 9% D.I. water qs. qs pH regulators (caustic sufficient to raise pH sufficient to raise pH soda and/or ammonia) pH 2.8 2.8 2.8
• a fog was applied at ratios of from 200 cc to 1,000 cc per ton of potatoes with an ultrasonic fogger (compressed air plus liquid) at a holding temperature of 3 to 4° C. at time intervals ranging from once a month up to every two weeks from 14 Feb. 2010 to May 2010.
• compositions were also applied to the potatoes by direct spray with the compositions described, with and without formic acid and with and without phosphoric acid.
• spraying applications the compositions were diluted at a ratio of 1:9 with tap water and applied at a volume of 2-10 liters per 1 ton of potatoes with or without 0.1%-2% surfactant on the cleaning, sorting and packing line.
• Tables 4 and 5 The results are summarized in the following Tables 4 and 5.
• composition A As can be seen in above Table 5, all varieties of potatoes, other than Blazer, reached an unacceptable rating of 3 by February 23 without treatment. In contrast, the treated samples (Table 4) suppressed sprouts in all varieties with the addition of a peroxide treatment (composition A), and then kept the same or better score following subsequent treatments with the inventive composition (composition B). For example, the W2310 and Silverton varieties unexpectedly showed a lower score following the formic acid treatment, indicating a reduction in the sprouting of the tubers.
• Mandarin oranges were treated shortly after harvest with compositions comprising performic acid, water, or an Imazalil composition, and then stored at 2° C. After 22 days, the number of rotten fruits, and the percent decay were assessed. A second trial was conducted with ten tons of mandarin oranges treated with a performic acid composition or Imazalil and stored and then stored at 2° C. The study was repeated with Red Grapefruit.
• the compositions comprising performic acid and the manner of applying the compositions varied throughout the course of the study within the parameters summarized in Table 6.
• compositions were applied to the citrus at room temperature with a fine spray of the performic acid containing composition and then treated either a) with a drain wash of water (either cold or heated to 55° C.) with a 1:9 dilution in tap water of the composition without formic acid, or b) with a drain wash of water (either cold or heated to 55° C.), followed by a fine spray at room temperature with a formulation identical to the perfomic acid formulation but without formic acid.
• a drain wash of water either cold or heated to 55° C.
• a drain wash of water either cold or heated to 55° C.
• the inventive method resulted in a lower level of decay in both mandarin oranges and Red Grapefruit, with reduced levels of chemical residue, in comparison to the prior art fungicidal treatment or water treatment.
• compositions were prepared, as described in Table 8 below (percentages are given in weight percent), and applied to seeds.
• compositions Composition Ingredients Control 9 8 7 6 5 4 3 2 1 H 2 O 2 (%) 10 10 10 10 5 10 10 10 10 10 H 3 PO 3 (%) 3 1 1 3 1 1 1.5 1.5 2 3 (COOH) 2 (%) 1 1 1.5 HCOOH (%) 3 3 1 1 1.5 H 3 BO 3 (%) 1 ZnSO 4 (%) 0.01 CUSO 4 (%) 0.01 Ag (ppm) 250 250 250 250 250 250 250 500 250 Benzoic Acid(%) 0.10 Sorbic Acid (%) 0.10 Glycerin(%) 2 2 2 HEDP(%) 0.5 0.5 0.5 1 1 1 1 1 0.5 Alcohol (%) 2 Surfactants 0.10 + +
• a concentrated aqueous 20% H 2 O 2 solution was prepared containing H 2 O 2 20%, phosphonic acid 8.0%, phosphoric acid 2.0%, glycerin 6.0%, silver 300 ppm.
• the H 2 O 2 concentration was checked: 20.1%.
• a portion of the solution was placed in an incubator at 55° C. and a portion was stored at room temperature.
• To 95.5 g of the solution at 55° C. were added 4.5 grams of HEDP from a European supplier. The solution was checked for the H 2 O 2 concentration therein:
• each of the two 5 liter solutions was diluted in 20 liters of tap water; a white precipitate formed.
• the efficacy of the solution was tested as follows: 150 kg of mandarins were divided into mesh bags and then sequentially submerged and shaken in the cold liquid so that each bag had the same contact time with cold liquid (about 60-90 seconds from initial immersion until the bag reached the next station in the production line). Next, each bag was submerged for about 30 seconds at 50° C. in the hot solution. The bags with the mandarins were then placed in a large container, from which they were transferred to the production line. At the next station they were passed through a dehydration cell, in which they were blown with hot air, after which they were waxed, hand sorted and packed in 10 cartons of 16 kg each.
• the goal was to form 20 liters of concentrated solution with the addition of a surfactant and to compare the activity of this surfactant-containing material to the activity of material without a surfactant.
• a surfactant To a 1% phosphonic acid solution was added silver to a concentration of 2 ppm. A solution of 50% NaOH was mixed in until the pH of the solution was 3.8. A portion of this was separated and to that portion was mixed in an alkyl glycoside surfactant to a concentration of 0.1%.
• 3 sweet potatoes were sprayed 7 times at intervals of 15-20 minutes with the non-surfactant solution and 3 sweet potatoes were sprayed 7 times with surfactant-containing solution; the vegetables were sprayed until dripping, then allowed to dry before being sprayed again. The effect of spraying was checked afterward; the treatment significantly improved shelf life and appearance. It was noted that there was a problem with foaming in the nozzles of the sprayer.
• the goal of this experiment was to prepare 1.5 liters of a solution containing 0.1% silver, 7.5% phosphonic acid and 5.0% hydrogen peroxide; the solution could then be 5-fold diluted prior to use.
• Into 1155 g of water were mixed 112.5 g phosphonic acid; the pH value of the solution at this stage was 1.2. The pH value was raised to 2.5 by addition of 50 ml of 50% sodium hydroxide solution with mixing. This was an exothermic process.
• Into the resulting hot solution was added 7.5 g surfactant (alkyl polyglycoside), mixed until fully dissolved. After allowing to cool, to the solution were added 150 g of 50% H 2 O 2 in which was dissolved 8.6 g stabilizer-containing silver solution.
• Solutions 1 and 3 were prepared. The solutions were prepared without raising the pH and without formic acid; before use it is necessary to add to each bottle 40 ml (50 g) of 95% formic acid.
• Solution 1 H 2 O 2 concentration before addition of formic acid was 7.4%, pH was not raised.
• Solution 2 not prepared.
• Solution 3 H 2 O 2 concentration before addition of formic acid was 7.3%, benzoic acid was not added (doesn't dissolve in the solution), surfactant (alkyl polyglycoside) was added, the pH was not raised.
• Solution 4 formic acid was added immediately during preparation, pH was not raised, surfactant was not added, H 2 O 2 concentration immediately after addition of formic acid was 7.03%. The solution was transferred to a closed bottle and the rate of performic acid formation checked. After 90 minutes the solution in the bottle was checked, the bottle expanded slightly, and the H 2 O 2 concentration was 6.6%, i.e. a 5.7% drop in concentration. H 2 O 2 concentration was still 6.6% after four days.
• Solutions 1 and 4 were sprayed on young potatoes. Results versus control: with solution 1, potatoes gained a brown tint (it should be noted that solution 1 was sprayed as-is without dilution with formic acid, i.e. the H 2 O 2 concentration was 7.4%). With solution 4, the tint of the potatoes was browner than the control but less brown than with solution 1 (note that the concentration of the H 2 O 2 at the time of spraying was 6.6%).
• Solution no. 5 was prepared containing 5.56% H 2 O 2 , 2.4% phosphoric acid, 100 ppm silver, 0.8% sulfuric acid, 4.0% formic acid, and water to complete to 100%. Phytotoxic injuries were observed on the potatoes that were sprayed with solution 5.
• Solution 5 was diluted two-fold to yield solution 5A; solution 5A was diluted two-fold to yield solution 5B. These solutions were sprayed on potatoes.
• Solution 6 was prepared; this is like solution 4 but the H 2 O 2 /formic acid ratio was 1:1 and not like solutions 4, 5 and their derivatives, in which the ratio was is 3:7.
• Solution 6 50 g 3.0% H 2 O 2 , 30 g 3.0% phosphoric acid, 0.57 g 100 ppm silver, 10 g 1.0% sulfuric acid, 30 g 3.0% formic acid, 880 g water to fill to 100%.
• the solution was left for 60 minutes after preparation and afterward sprayed on potatoes. Phytotoxic injuries were observed on potatotes, but these were attributed to the variety of potato used (Vivaldi) which is an incomplete skin variety in which skin injuries are known to occur. The experiment was discontinued.
• ingredients were mixed in the order recited; in cases in which hydroxide was added to an acidic mixture to raise the pH, this resulted in an exothermic reaction which raised the temperature of mixture.
• SpuDefender Classic (preparation of 2000 g): 60% hydrogen peroxide, 223 g (7% in the final preparation); 85% phosphoric acid, 82.3 g (3.5% in the final preparation); silver solution, 1.6 g (140 ppm silver in the final preparation); remainder distilled water (1683.1 g)
• Classic+F SpuDefender (preparation of 2000 g): 60% hydrogen peroxide, 223 g; 85% phosphoric acid, 82.3 g; silver solution, 1.6 g (140 ppm in the final preparation); 60 g formic acid (3.0% in the final preparation); remainder distilled water (1623.1 g).
• SpuDefender Natural (preparation of 2000 g): 60% hydrogen peroxide, 223 g; formic acid, 60 g (3.0% in the final solution); remainder distilled water (1705.4 g).
• SpuDefender Natural/2 after waiting 2 hours to allow formation of performic acid in the SpuDefender Natural solution, this solution was diluted to half strength by addition of an appropriate amount of water to yield the title solution.
• SpuDefender Joker this was prepared like the Classic SpuDefender solution, except the concentration of phosphoric acid in the final preparation was 7.5%.
• SpuDefender Joker+F this was like the Classic+F SpuDefender solution, except the concentration of phosphoric acid in the final preparation was 7.5%; it was prepared by mixing 45 g formic acid into 1455 g SpuDefender Joker.
• Performic acid-containing solutions A working solution of 3 liters at pH 2.8 having the following concentrations was prepared: 2% phosphonic acid, 2.0% BLS, 0.5% Glycerin, 0.1% alkyl polyglycoside.
• a concentrated solution of 1 liter was prepared containing 20% phosphonic acid; the solution should be diluted with 9 parts water to obtain a 2% phosphonic acid solution or with 19 parts water to obtain a 1% phosphonic acid solution.
• the concentrated solution should contain 20% BLS, 2% H 2 O 2 , 5.0% glycerin, and 1.0% surfactant at pH 2.8.
• volume of each solution was 500 ml.
• this solution did not contain phosphonic or phosphoric acids, and the concentration of formic acid was increased from 3% to 5%.
• the formulation was applied by spraying (hand spray till dripping) to table potatoes of various varieties: Lady Rosetta, Morris Pfeifer, Nicola. Five days after application and storage at room temperature, the potatoes were checked. There was slight phytotoxicity in places on the potatoes where the applied formulation didn't dry (for example due to contact with other surfaces), but as desired there was blackening, shrinking and drying of the sprouts. In one of the potatoes of the Nicola variety new white pips were observed.
• Sol2/2 Solution contains formic acid, dilutions were made on-site shortly before use.
• SOL2B/2B solution contains formic acid but not glycerin, dilutions were made on-site shortly before use.
• SOLS solution contains formic acid, dilutions were made on-site shortly before use.
• SOL4 solution contains formic acid, dilutions were made on-site shortly before use; there were only 270 grams of solution.
• a solution containing (after dilution) phosphonic acid 0.8%, H 2 O 2 1%, silver 15 ppm, formic acid 0.5% was prepared.
• To 4.8 liters of concentrated solution were added 0.2 liters of formic acid.
• Formulation for concentrated solution phosphonic acid 8%, NaOH 100% (solid): approximately 4%; 50% H 2 O 2 , 20%; silver 150 ppm; formic acid: 5%; alkyl polyglycoside 0.2%, remainder distilled water to 100%
• Solution 1 25 kg were prepared as follows: phosphonic acid, 2.68 kg of 70% solution; NaOH 47%, 2.0 kg; H 2 O 2 50%, 2.5 kg; 17% silver solution 0.015 kg; 85% formic acid, 0.625 kg; alkyl polyglycoside 0.04 kg; distilled water 17.175 kg. Following this, 1.5 parts solution were diluted with 8.5 parts water. Concentration of materials after dilution: phosphonic acid: 1.12%, H 2 O 2 0.75%, silver 16 ppm, formic acid 0.375%. In order to prepare the solution before dilution, to 3.0 kg of concentrated solution were added 75 g of formic acid.
• Solution 2 25 kg were prepared as follows: phosphonic acid, 2.15 kg of 70% solution; NaOH 47%., 1.5 kg; H 2 O 2 50%, 7.5 kg; 17% silver solution, 0.02 kg; 85% formic acid, 1.65 kg; distilled water 11.64 kg. Following this, 1 part solution was diluted with 9 parts water. Concentration of materials after dilution: phosphonic acid, 0.602%; H 2 O 2 , 1.5%; silver, 14 ppm; formic acid: 0.66%. In order to prepare the solution before dilution, to 2 kg of concentrated solution 141.3 g of formic acid were added.
• stable formulations of performic acid are also provided in accordance with embodiments of the invention. While such formulations, like the performic acid-containing formulations described in the examples above, may be formulated on-site just prior to use, for example by adding one of the reactive ingredients (e.g. H 2 O 2 , ozone, or formic acid) shortly before use, in some embodiments of the present invention the formulations may be formulated off-site and stored, without significant loss of performic acid during storage.
• the reactive ingredients e.g. H 2 O 2 , ozone, or formic acid
• Such stable formulations may be made in concentrated form, so that an end user may dilute the formulation with tap water, for example in ratio of concentrated formulation:water of 1:1, 1:2, 1:5, 1:10, 1:20, 1:30, 1:50 ,1:70, 1:100, 1:120, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450, or 1:500, to obtain a working solution on-site.
• pre-mixes to which one of the reactive ingredients may be added on-site to make the performic acid just prior to use. The following examples illustrate some such stable performic acid-containing compositions.
• a composition was prepared containing H 2 O 2 , phosphonic acid which had been partly neutralized with KOH, formic acid, citric acid, and one or more alkyl polyglycoside surfactants; as will be appreciated by persons skilled in the art, performic acid is formed in situ. It was found that stable, concentrated solutions, which may later be diluted on-site just prior to use, may be formed when the concentration of H 2 O 2 (or other oxidizer, e.g. ozone) in the mixture is approximately 15 wt. %, and the concentration of formic acid is approximately 10-12 wt.
• H 2 O 2 or other oxidizer, e.g. ozone
• these concentrations may be as follows:
• H 2 O 2 in some embodiments the concentration of H 2 O 2 , prior to addition to the mixture in which performic acid is formed, is at least 0.1% by weight. In some embodiments the concentration is at least 0.2 wt. %. In some embodiments the concentration is at least 0.25 wt. %. In some embodiments the concentration is at least 0.3 wt. %. In some embodiments the concentration does not exceed 70 wt. %. In some embodiments the concentration does not exceed 50 wt. %. In some embodiments the concentration does not exceed 35 wt. %. In some embodiments the concentration does not exceed 20 wt. %.
• the H 2 O 2 concentration, prior to addition to the mixture in which performic acid is formed is from 0.1 wt. %-70 wt. %. In some embodiments the H 2 O 2 concentration is from 0. wt.2%-50 wt. %. In some embodiments the H 2 O 2 concentration is from 0.25-35 wt. %. In some embodiments the H 2 O 2 concentration is from 0.3-20 wt. %. In some embodiments the H 2 O 2 concentration is from 3%-15 wt. %. It will also be appreciated that when other compounds are used as oxidizers they may included in concentrations similar to those listed above.
• the formic acid concentration is at least 3 wt. %. In some embodiments, the formic acid concentration is at least 5 wt. %. some embodiments, the formic acid concentration is at least 10 wt. %. In some embodiments, the formic acid concentration is not more than 70 wt. %. In some embodiments, the formic acid concentration is not more than 50 wt. %. In some embodiments, the formic acid concentration is not more than 35 wt. %. In some embodiments, the formic acid concentration is not more than 25 wt. %. Also, when formic acid is used, it has been found that using a 1:1 ratio of formic acid to hydrogen peroxide gives very stable results.
• Phosphonic acid partly neutralized: in some embodiments, the phosphonic acid is partly neutralized before its addition to the mixture in which the performic acid is formed. In some embodiments, the partial neutralization is carried out using KOH. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 1. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 1.5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 1.7. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 2. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 2.5.
• the phosphonic acid is partly neutralized to a pH of not less than 3. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 3.5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 10. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 9. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 7. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 4.5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 4.0.
• the phosphonic acid is first partly neutralized to a pH of 1-10. In some embodiments, the phosphonic acid is partly neutralized to a pH 1.1-9. In some embodiments, the phosphonic acid is partly neutralized to a pH of 1.2-7. In some embodiments, the phosphonic acid is partly neutralized to a pH 1.5-5. In some embodiments, the phosphonic acid is partly neutralized to a pH of 2-4.5. In some embodiments, the concentration of the phosphonic acid, prior to addition to the mixture in which performic acid is formed, is at least 0.1 wt. %. In some embodiments, the concentration is at least 0.2 wt. %. In some embodiment the concentration is at least 0.3 wt. %.
• the concentration is at least 0.5 wt. %. In some embodiment the concentration is at least 0.75 wt. %. In some embodiments, the concentration of the phosphonic acid, prior to addition to the mixture in which performic acid is formed, is not more than 70 wt. %. In some embodiments, the concentration is not more than 50 wt. %. In some embodiments, the concentration is not more than 35 wt. %. In some embodiments, the concentration is not more than 20 wt. %. In some embodiments, the concentration of the phosphonic acid, before addition to the mixture in which the performic acid is formed, is from 0.1%-70%. In some embodiments the concentration is from 0.2%-50%. In some embodiments the concentration is from 0.3-35%.
• the concentration is from 0.75%-25%. In some embodiments the concentration is from 0.5-20%. It will also be appreciated that in some cases, solid phosphonic acid, a salt thereof, or mixtures thereof, e.g. in granulated form, may be used. It will also be appreciated that the dissolution of solid phosphonic acid in water is endothermic, as is the dissolution of KOH, whereas the mixing of solutions of KOH and phosphonic or other dissolved acids is exothermic. Hence, persons skilled in the art will readily appreciate ways in which the order of addition of ingredients may be manipulated to achieved desired temperature effects.
• Citric acid in some embodiments, the concentration of citric acid, prior to addition to the mixture in which the performic acid is formed, is at least 0.1 wt. %. In some embodiments the concentration is at least 0.15 wt. %. In some embodiments the concentration is at least 0.2 wt. %. In some embodiments the concentration is at least 0.25 wt. %. In some embodiments the concentration is at least 0.3 wt. %. In some embodiments the concentration is at least 0.5 wt. %. In some embodiments the concentration is not more than 50 wt. %. In some embodiments the concentration is not more than 40 wt. %. In some embodiments the concentration is not more than 30 wt. %.
• the concentration is not more than 20 wt. %. In some embodiments the concentration is about 15 wt. %. In some embodiments the concentration of the citric acid, before addition to the mixture in which the performic acid is formed, is from 0.1%-50%. In some embodiments the concentration is from 0.15-40%. In some embodiments the concentration is from 0.2-30%. In some embodiments the concentration is from 0.25-20%. In some embodiments the concentration is from 0.3-10%.
• citric acid was used, other carboxylic acids may be used to the same effect, for example C 2 -C 7 carboxylic acids such as propionic acid, lactic acid, salicylic acid, benzoic acid, glyceric acid, oxalic acid, tartaric acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and trifluoroacetic acid, and that these may be used in similar concentrations. Mixtures of carboxylic acids may also be used. It will also be appreciated, that as with phosphonic acid, the citric and/or other carboxylic acid may be provided in solid form and dissolved directly as needed.
• C 2 -C 7 carboxylic acids such as propionic acid, lactic acid, salicylic acid, benzoic acid, glyceric acid, oxalic acid, tartaric acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and trifluoroacetic
• Alkyl polyglycoside surfactant(s) alkyl polyglycoside surfactants for agricultural use are known in the art.
• the total concentration of alkyl polyglycoside surfactants in the mixture in which the performic acid is formed is at least 0.001 wt. %. In some embodiments the concentration is at least 0.01 wt. %. In some embodiments the concentration is at least 0.1 wt. %. In some embodiments the concentration is at least 1 wt. %.
• surfactants may include amphoteric surfactants, cationic surfactants, non-ionic surfactants, and anionic surfactants.
• the composition may be used as a disinfectant in and on food commodities, for soil, water, surfaces, equipment, air volumes, plant matter, and feed stocks, including disinfection and sterilization needs in all fields of application.
• compositions e.g. for Arresting Sprouting in Potatoes
• compositions were formed in a manner similar to that of Example 20, various compositions were formed.
• one or more ingredients such as formic acid, were left out of the composition and only added on-site prior to use.
• phosphoric acid was used in addition to or instead of phosphonic acid.
• Such compositions were found to be stable and efficacious, for example in arresting sprouting of potatoes.
• the total concentration of phosphoric acid, prior to addition to the mixture in which the performic acid is formed, is at least 0.1 wt. %. In some embodiments the concentration is at least 0.2 wt. %. In some embodiments the concentration is at least 0.3 wt. %. In some embodiments the concentration is at least 0.5 wt. %. In some embodiments the concentration is not more than 70 wt. %. In some embodiments the concentration is not more than 50 wt. %. In some embodiments the concentration is not more than 35 wt. %. In some embodiments the concentration is not more than 20 wt. %.
• the concentration of phosphoric acid, before addition to the mixture in which the performic acid is formed is from 0.1-70 wt. %. In some embodiments the concentration is from 0.2-50 wt. %. In some embodiments the concentration is from 0.3-35 wt. %. In some embodiments the concentration is from 0.5-20 wt. %. In some embodiments the concentration is around 10 wt. %.
• potassium bicarbonate may be added as well in order to generate additional CO 2 ; such a method is particularly effective if application of the formulation will be made in a closed storage space via fogging or in the gas phase.
• gaseous ozone is used as an oxidizer to form performic acid in the gas phase, excess ozone can be supplied, as ozone itself may also help control pathogens.
• KOH potassium metabisulfite or potassium permanganate
• these are also known to function as preservatives.
• a mixture (Mixture 1) containing 51.65 wt. % deionized water, 21.4 wt. % of 47% aqueous KOH solution, 11.8 wt. % of 85% formic acid solution, 14.1 wt. % of 70% phosphonic acid solution, 1.0 wt. % Dequest® 2010 (1-hydroxyethylidene-1,1-diphosphonic acid), and 0.05 wt. % alkyl glycoside was prepared. To four parts by weight of Mixture 1 were mixed one part of 50% H 2 O 2 solution. For testing, this mixture was further diluted 100-fold in water.
• EN 1276 defines a bactericidal product that has the capability to produce at least a 10 5 reduction in the number of viable cells of the tested organisms, under defined experimental conditions.
• a test suspension of bacteria in a solution of 0.3% bovine albumin to act as an interfering substance was added to the diluted product.
• the mixture was maintained at 20° C.-23° C. for 1 min. (the smallest of the recommended contact times according to the standard, which recommends longer contact times 10 or even 15 minutes), then the bactericidal action of the product was neutralized by the membrane filtration method, and the number of surviving bacteria was determined.
• Bacteria used were Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), and Enterococcus hirae (ATCC 10541). Each bacterial strain was maintained and counted by the pour plate method in accordance with EN 1276:1997. Experimental conditions were as follows:
• the Membrane Filtration method was used for assessing the bactericidal effect of the product, and the results are summarized in the table immediately below.
• Validation tests are summarized in the table immediately below. Verification of the methodology for each test organism shows that: (a) the number of cfu/ml of the bacterial test suspension is between 1.5 ⁇ 10 8 and 5.0 ⁇ 10 8 cfu/ml (N in the table above); (b) the number of cfu/ml of the bacterial suspension is between 6.0 ⁇ 10 2 and 3.0 ⁇ 10 3 cfu/ml (Nv in the table below); (c) the number of cfu/ml of the neutralizer toxicity control (B in the table below) is equal to, or greater than 0.05 times the number of cfu/ml of the bacterial suspension (Nv in the table below); (d) The number of cfu/ml of the dilution-neutralization control (C in the table below) is equal to, or greater than 0.5 times the number of cfu/ml of the neutralizer toxicity control (B in the table below); (c) the number of
• the tested composition possesses bactericidal activity in one minute at 20° C. under dirty conditions (3.0 g/l bovine albumin) for the tested reference strains.
• EN 1650 specifies a test method and the minimum requirements for anti-fungal, anti-yeast and anti-mold activity of chemical disinfectant and antiseptic products that form a homogeneous, physically stable preparation in hard water and that are used in food, industrial, domestic and institutional areas, excluding areas and situations where disinfection is medically indicated and excluding products used on living tissues except those for hand hygiene in the above-considered areas.
• fungicidal activity is the capability of a product to produce at least a 10 4 reduction in number of the vegetative yeast cells and mold spores belonging to the reference strains Candida albicans (ATCC 10231), Aspergillus niger (ATCC 16404) and Penecillium w.t. (wild type) under conditions defined by this standard.
• a test suspension of yeast cells and/or mold spores in a solution of interfering substance (bovine albumin, 3 g/l) was added to a prepared sample of the product under test diluted in hard water. The mixture was maintained at 20° C. ⁇ 1° C. for 1 min ⁇ 10 s (required test conditions). After this contact time, an aliquot was taken; the fungicidal action in this portion was immediately neutralized or suppressed by a validated method. The method of choice was dilution-neutralization. (If a suitable neutralizer could be found, membrane filtration was used.) The number of surviving fungi, yeast cells or mold spores in each sample was determined and the reduction in viable counts was calculated.
• interfering substance bovine albumin, 3 g/l
• test temperature 20° C. ⁇ 0.5° C.; concentration of test product 1:99, diluted in water; contact time 1 minute; interfering substance 3.0 g/l bovine albumin; neutralizing solution 30 g/l saponin, 30 g/l polysorbate 80, 1 g/l L-histidine, 1 g/l L-cysteine; incubation temperature 30° C.+1° C.
• the tested formulation possesses satisfactory fungicidal activity in 1 minute at 20° C. under dirty conditions (3 g/l bovine albumin) for the tested reference strains.
• PAA peracetic acid
• the formulation in accordance with the present invention was 10-100 times more effective than PAA in killing A. niger and Penicillium.
• Aqueous solutions of 50% H 2 O 2 and 42% citric acid were mixed in a 3:2 ratio, yielding a mixture with 30 wt. % H 2 O 2 and 16.8 wt. % citric acid. This was then mixed in a 1:1 ratio with Mixture 1 from Example 22. The resulting mixture was tested for stability by measuring the concentrations of H 2 O 2 and formic acid over time. The loss of H 2 O 2 over three months of storage at room temperature was about 0.5%, i.e. the H 2 O 2 concentration was nearly unchanged over this period.
• Solutions were prepared according to the table below and used in amounts of 10.7 ml to treat 100 g of soil of pH 8 by mixing therein until a paste was obtained; except for trial 1, the soil was pre-wetted with 10.7 ml of water. Samples of soil were then taken for titration at the intervals shown. In the first table. units are wt. % unless noted otherwise.
• compositions (solutions) containing performic acid were prepared as discussed in the preceding examples; in some cases the compositions included one or more of the following groups: Emulsifiers, chelating agents, lubricants, corrosion inhibitors, anti foaming agents, inorganic additives, organic additives, modifiers, promoters, synergists, activators, solvents, essential oils, other ingredients, pH regulators, bases, acids, wetting agents, surfactants, stabilizers, catalysts, oxidizers, and performic Acid sources.
• Emulsifiers Emulsifiers, chelating agents, lubricants, corrosion inhibitors, anti foaming agents, inorganic additives, organic additives, modifiers, promoters, synergists, activators, solvents, essential oils, other ingredients, pH regulators, bases, acids, wetting agents, surfactants, stabilizers, catalysts, oxidizers, and performic Acid sources.
• compositions are in a liquid phase they may be applied them by immersing the substance to be treated in the compositions, and/or spraying the substance with the compositions, and/or creating a fog made of micro droplets using ultrasonic air pressure/liquid fogger and/or electric ultrasonic resonance, with or without heating, with or without ozone gas and/or ozonated water.
• the gas phase is introduced with a hot fogger with or without ozone gas.
• Oxidizing levels are measured rapidly on site with a certified field kit. As of today there is no certified field kit to measure the performic acid (PFA) levels, so the inventor developed a standard measuring constant that correlates to the oxidation rate: using a Reflectoquant Colorimeter (Merck), the concentration of H 2 O 2 and/or PAA was measured; a correlation constant was calculated to enable computation of the PFA concentration. As a parallel control titration of the solutions as described by Swern at al. (Organic Peroxides 1 (1970) p. 501) was conducted in a laboratory.
• the disinfection treatments yielded 3-7% more hatched chicks; 4e Herbicide; 4f Insecticide, Miticide/acaricide, Nematocide; 4g Rodenticide; 4h Elimination of cut-end blackening, inducing whitening—such as but not limited to cut corn, celery, lettuce, French fries and all fresh cut produce, including chilled ready to eat salads and other chilled meals; 4i Improve storability and prolong shelf life—this addresses in a more specific category produce that is kept under long storage periods (weeks and months) that suffers losses during the storage period and later on: as the physiological age progresses, the produce becomes more prone to any stress, with the outcome being a very short shelf life; 4j Improve yield—this addresses seeds yield, orchard yield, soil yield after treatments, chick yield from fertilized eggs, etc.
• 6a warmed solution 25-90° C.; 6b ambient solution 20-25° C.; 6c cooled solution 0.1-20° C.
• Contact time/application time contact time is the time the composition is in contact with the treated matter; application time is the time required for the solution to be applied to the matter. For example, a fruit is sprayed for 5 seconds (application time) and the solution is washed after 40 seconds of contact with the sprayed composition (contact time).
• 9a at the entry to the long storage and or to the packing house; 9b during storage before sorting line treatment; 9c on sorting line treatment; 9d during storage after sorting line treatment; 9e right before packing
• a first and a second mixture were mixed together in a ratio of 40 wt. % first mixture and 60 wt. % second mixture, along with phosphonic acid.
• the first mixture contained 80 wt. % of a 94 wt. % aqueous formic acid solution and 20 wt. % of a 99 wt. % propionic acid solution.
• the second mixture was a 50 wt. % hydrogen peroxide solution. For testing, this mixture was further diluted 1000-fold in water; the resulting dilute solution (which contained about 800 ppm of phosphonic acid) had a pH of approximately 2.5.
• EN 1276 defines a bactericidal product that has the capability to produce at least a 10 5 reduction in the number of viable cells of the tested organisms, under defined experimental conditions.
• a test suspension of bacteria Lysteria monocytogenes, ATCC 19115
• 3 g/l bovine albumin to act as an interfering substance
• the composition used was the same composition described in Example 22; as in Example 22, for testing it was diluted 100-fold.
• EN 13697 specifies a test method for testing the efficacy of materials against microorganisms on surfaces.
• a test suspension of fungi in solution under dirty conditions is inoculated onto a stainless steel surface and dried.
• the prepared sample of the product is applied in a manner which covers the dried film.
• the surface is maintained at a specified temperature for the defined contact time.
• the surface is transferred to the neutralization medium.
• the number of surviving organisms which can be recovered from the surface is determined. Dilution-neutralization is also utilized in parallel in some of the samples.
• the fungal strain was maintained and counted by the pour plate method in accordance with EN 13697:2001.
• Experimental conditions test temperature, 22° C. ⁇ 1° C.; contact times 1 minute and 5 minutes; hard water (distilled, not demineralized water), per total volume of 1000 ml: 0.12 g of anhydrous MgCl 2 , 0.28 g of anhydrous CaCl 2 , and 0.28g of NaHCO 3 were added; interfering substance: 3.0 g/l bovine albumin—dirty conditions; neutralizer: 6 g/l sodium thiosulphate+30 g/l polysorbate 80+lecithin 3 g/l; temperature of incubation 30° C. ⁇ 1° C.; test surface: stainless steel discs (2 cm diameter); test procedure: dilution-neutralization method was used to assess the fungicidal effect of the product, and the results are summarized in the table below.
• KEF 1 possesses fungicidal activity on surfaces in 1 min and in 5 min at 22° C. under dirty conditions (3 g/l bovine albumin) for reference strain of Aspergillus brasiliensis.

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