WO2008089089A2 - Microbiocidal treatment of edible fruits and vegetables - Google Patents

Microbiocidal treatment of edible fruits and vegetables Download PDF

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Publication number
WO2008089089A2
WO2008089089A2 PCT/US2008/050901 US2008050901W WO2008089089A2 WO 2008089089 A2 WO2008089089 A2 WO 2008089089A2 US 2008050901 W US2008050901 W US 2008050901W WO 2008089089 A2 WO2008089089 A2 WO 2008089089A2
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WIPO (PCT)
Prior art keywords
bromine
composition
microbiocidal
dihalo
dialkylhydantoin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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PCT/US2008/050901
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English (en)
French (fr)
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WO2008089089A3 (en
Inventor
Joe D. Sauer
George W. Cook, Jr.
William S. Pickrell
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Albemarle Corp
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Albemarle Corp
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Publication date
Application filed by Albemarle Corp filed Critical Albemarle Corp
Priority to US12/517,646 priority Critical patent/US20100035950A1/en
Priority to BRPI0806247-1A priority patent/BRPI0806247B1/pt
Priority to JP2009545711A priority patent/JP5337710B2/ja
Priority to CN2008800020421A priority patent/CN101578048B/zh
Publication of WO2008089089A2 publication Critical patent/WO2008089089A2/en
Publication of WO2008089089A3 publication Critical patent/WO2008089089A3/en
Anticipated expiration legal-status Critical
Priority to US13/739,087 priority patent/US9629376B2/en
Ceased legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B7/00Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154Organic compounds; Microorganisms; Enzymes
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00Preservation of foods or foodstuffs, in general
    • A23B2/70Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729Organic compounds; Microorganisms; Enzymes
    • A23B2/762Organic compounds containing nitrogen
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B7/00Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157Inorganic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • This invention relates to use of effective antimicrobial solutions for controlling contamination of edible fruits and vegetables by various pathogens such as species of Listeria, Escherichia, Salmonella, Campylobacter, and others.
  • pathogens such as species of Listeria, Escherichia, Salmonella, Campylobacter, and others.
  • the term "edible fruit and vegetable”, whether used in the singular or plural, denotes any harvested or unharvested edible uncooked fruit or vegetable that is grown for consumption by humans.
  • U.S. Pat. No. 6,660,310 describes a method of infusing edible fresh or freshly cut fruit or vegetable. The fruit or vegetable is allowed to reach a state of relative metabolic stasis or inactivity. An infusion comprising an agent to be infused is provided and the fruit or vegetable is submerged therein or coated therewith.
  • agents referred to are an aroma enhancing agent, a flavor enhancing agent, a sweetening agent, a color- enhancing agent, a nutritionally beneficial agent, a phytochemical, a pharmaceutical agent, etc.
  • the infusion is pressurized to a positive or negative pressure for a period of time.
  • the patent indicates that preferably, the surface of the fruit or vegetable is disinfected with a bleach solution and/or an antimicrobial soap solution and that more preferably, the solution has a concentration in the range of about 0.01% to about 10%, and most preferably, the solution has a concentration of about 2%.
  • a listing of materials used in experimental approaches indicates that either Clorox® Bleach (distributed by The Clorox Company of Oakland Calif.) in a 2% solution, or Safesoap® antimicrobial liquid hand soap (distributed by Colgate-Palmolive Company of New York, N. Y.) in a 2% solution were used.
  • This invention provides a new way of controlling bacterial, yeast, and/or mold contamination of edible fruits and vegetables at any of a variety of points in the production, processing, distribution or marketing of edible fruits and vegetables.
  • the method involves a simple application of a highly effective stabilized microbiocide followed by a brief residence time of the microbiocide on the fruit or vegetable followed by a suitable washing procedure.
  • the amount of the biocide used is less than that described in the above patent.
  • the aqueous microbiocidal composition applied to the edible fruit or vegetable is stabilized against ultraviolet light-induced degradation.
  • this embodiment is a method of controlling bacterial, yeast, and/or mold contamination of at least one edible fruit or vegetable, which method comprises applying to the edible fruit or vegetable an aqueous microbiocidal composition stabilized against ultraviolet light-induced degradation and containing less than 100 ppm (wt/wt) of active bromine formed from ingredients comprising water and: A) at least one microbiocidal component selected from:
  • compositions having an active bromine content of at least 50,000 ppm, which composition is formed from components comprising water and (i) bromine chloride or bromine chloride and bromine, with or without conjoint use of chlorine and (ii) overbased alkali metal salt of sulfamic acid and/or sulfamic acid, alkali metal base, and water, wherein the relative proportions of (i) and (ii) are such that the atom ratio of nitrogen to active bromine is greater than 0.93, and wherein the pH of the composition is greater than 7;
  • the selected components of A) and B) can be mixed with the water either separately or as a preformed mixture.
  • the applied aqueous microbiocidal composition is allowed to remain in contact with the edible fruit or vegetable for a microbiocidally- effective period, which typically is in the range of about 10 seconds to about 30 minutes, and preferably in the range of about 30 seconds to about 5 minutes, and then the edible fruit or vegetable is thoroughly washed at least once with water which, optionally, contains at least one surfactant.
  • a microbiocidally- effective period typically is in the range of about 10 seconds to about 30 minutes, and preferably in the range of about 30 seconds to about 5 minutes, and then the edible fruit or vegetable is thoroughly washed at least once with water which, optionally, contains at least one surfactant.
  • the higher the concentration of bromine in the aqueous microbiocidal composition used the shorter should be the time the microbiocidal composition is allowed to be in contact with the edible fruit or vegetable.
  • the one or more washes that are utilized should be thorough enough to at least remove any and all detectable quantities of the antimicrobial composition from the treated edible fruit or vegetable. If a surfactant is used in one or more such washes, one or more subsequent water washes are to be employed to ensure removal of the surfactant from the edible fruit or vegetable.
  • microbiocidal compositions utilized in the practice of this invention are solid-state microbiocidal compounds having at least one bromine atom in the molecule.
  • Such compounds are exemplified by (a) l,3-dihalo-5,5-dialkylhydantoins in which both of the halo atoms are bromine atoms and one of the alkyl groups is a methyl group and the other is a C 1 ⁇ alkyl group and by (b) l,3-dihalo-5,5-dialkylhydantoins in which one of the halo atoms is a bromine atom and the other is a chlorine atom, and both alkyl groups are, independently, Ci_ 4 alkyl groups.
  • solid-state microbiocidal compounds of (a) and (b) are more preferred than any other type of solid-state microbiocidal compound, and because of superior effectiveness, those of (a) are even more preferred, with 1,3-dibromo- 5,5-dimethylhydantoin being most preferred of all.
  • Non-limiting examples of compounds of type (a) include l,3-dibromo-5,5- dimethylhydantoin, 1 ,3-dibromo-5-ethyl-5-methylhydantoin, 1 ,3-dibromo-5-n-propyl-5- methylhydantoin, 1 ,3-dibromo-5-isopropyl-5-methylhydantoin, 1 ,3-dibromo-5-n-butyl-5- methylhydantoin, 1 ,3-dibromo-5-isobutyl-5-methylhydantoin, 1 ,3-dibromo-5-sec-butyl-5- methylhydantoin, l,3-dibromo-5-tert-butyl-5-methylhydantoin, and mixtures of any two or more of them.
  • l,3-dibromo-5-isobutyl-5-methylhydantoin 1,3- dibromo-5-n-propyl-5-methylhydantoin, and l,3-dibromo-5-ethyl-5-methylhydantoin are, respectively, preferred, more preferred, and even more preferred members of this group from the cost effectiveness standpoint.
  • l,3-dibromo-5,5- dimethylhydantoin as one of the components, with a mixture of l,3-dibromo-5,5- dimethylhydantoin and l,3-dibromo-5-ethyl-5-methylhydantoin being particularly preferred.
  • the most preferred member of this group of microbiocides is l,3-dibromo-5,5- dimethylhydantoin.
  • This compound is available in the marketplace in tablet or granular form under the trade designations XtraBrom® 111 biocide and XtraBrom® H IT biocide (Albemarle Corporation).
  • XtraBrom® 111 biocide XtraBrom® 111 biocide
  • XtraBrom® H IT biocide Albemarle Corporation
  • the individual biocides of the mixture can be in any proportions relative to each other.
  • Non-limiting examples of compounds of type (b) include N,N'-bromochloro-5,5- dimethylhydantoin, N,N'-bromochloro-5-ethyl-5-methylhydantoin, N,N'-bromochloro-5- propyl- 5 -methylhydantoin, N,N'-bromochloro-5-isopropyl-5-methylhydantoin, N,N'- bromochloro-5-butyl-5-methylhydantoin, N,N'-bromochloro-5-isobutyl-5- methylhydantoin, N,N'-bromochloro-5-sec-butyl-5-methylhydantoin, N,N'-bromochloro- 5-tert-butyl-5-methylhydantoin, N,N'-bromochloro-5,5-diethylhydantoin, and mixtures of any two or more of the fore
  • N,N'-bromochloro-5,5-dimethylhydantoin is available commercially under the trade designation Bromicide® biocide (Great Lakes Chemical Corporation).
  • Bromicide® biocide Great Lakes Chemical Corporation
  • Another suitable bromochlorohydantoin mixture is composed predominantly of N,N'-bromochloro-5,5-dimethylhydantoin together with a minor proportion by weight of l,3-dichloro-5-ethyl-5-methylhydantoin.
  • a mixture of this latter type is available in the marketplace under the trade designation Dantobrom® biocide (Lonza Corporation).
  • N,N'-bromochloro-5,5-dimethylhydantoin is a preferred material because of its commercial availability and its suitability for use in the practice of this invention.
  • the designation N,N' in reference to, say, N,N'-bromochloro- 5,5-dimethylhydantoin means that this compound can be (1) l-bromo-3-chloro-5,5- dimethylhydantoin, or (2) l-chloro-S-bromo-S ⁇ -dimethylhydantoin, or (3) a mixture of 1- bromo-3-chloro-5,5-dimethylhydantoin and l-chloro-3-bromo-5,5-dimethylhydantoin.
  • N,N'-dihalo-2-imidazolidinones such as l,3-dibromo-4,4,5,5-tetramethyl-2- imidazolidinone, l-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazolidinone, l-chloro-3- bromo-4,4,5,5-tetramethyl-2-imidazolidinone, l,3-dibromo-2,2,5,5- tetramethylimidazolidin-4-one, 1 -bromo-3-chloro-2,2,5,5-tetramethylimidazolidin-4-one, l-chloro-3-bromo-2,2,5,5-tetramethylimidazolidin-4-one.
  • Preparation of such compounds is described in U.S. Pat. Nos. 4,681,948; 4,767,542; and 5,057,
  • Still other known solid-state microbiocidal compounds which may be utilized are sulfonyloxy bromoacetanilides such as m-isobutyl-sulfonyloxy bromoacetanilide and m- phenyl- sulfonyloxy bromoacetanilide. Still other examples and the preparation of such compounds are given in U.S. Pat. No. 4,081,474.
  • bromine-containing alpha-halo pyruvate oximes such as described in U.S. Pat. No. 4,740,524.
  • examples of such compounds include ethyl 3-bromo-2-(4- chlorobenzoyloximino)propanoate, ethyl 3-bromo-2-(N'-methylcarbomoyloxi- mino)propanoate, and ethyl 3-bromo-2-(4-methylbenzoyloximino)propanoate.
  • Yet another type of solid-state bromine-containing microbiocidal compounds which can be used are non-polymeric quaternary ammonium polybromides described in U.S. Pat. No. 4,978,685.
  • examples of such compounds include N-ethyl-N, N, N- trimethylammonium tribromide; N-ethyl-N-methylmorpholinium tribromide; N-benzyl- N,N-dimethyl-N-myristylammonium dibromochloride; N, N, N, N-tetrabutylammonium tribromide; and N, N, N, N-tetrabutylammonium dibromochloride.
  • Group II constitutes another group of bromine-based microbiocidal compositions, one or more members of which can be utilized in the practice of this invention. These are aqueous solutions or slurries of at least one solid-state microbiocidal compound having at least one bromine atom in the molecule.
  • aqueous solutions or slurries of at least one solid-state microbiocidal compound having at least one bromine atom in the molecule can be used in forming these solutions or slurries.
  • the solutions can contain any concentration of the respective compounds up to their saturation points. If higher concentrations are desired, slurries containing quantities in excess of the respective saturation points can be formed and used.
  • the concentration of the solutions or slurries used are usually higher than the desired end use concentration in the washing solution applied to the fruit or vegetable.
  • Group III) of Bromine-Based Microbiocides are usually higher than the desired end use concentration in the washing solution applied to the fruit or vegetable.
  • a number of bromine -based microbiocides are typically formed and provided in the form of concentrated aqueous solutions, and these concentrated aqueous solutions constitute Group III) of the bromine-based microbiocides used pursuant to this invention.
  • Such microbiocides are typically stabilized against chemical decomposition and physical evaporation of active bromine species by the inclusion in the product during its formation of a suitable stabilizing component for the active bromine in the concentrated solution.
  • a preferred liquid state bromine-based biocide of this type is an aqueous biocide composition
  • This product also contains active bromine stabilized against chemical decomposition and physical evaporation of active bromine species by the inclusion of sulfamate.
  • active bromine stabilized against chemical decomposition and physical evaporation of active bromine species by the inclusion of sulfamate.
  • This group of bromine-based microbiocides is composed of solid-state microbiocidal compositions formed by dewatering (i.e., removing at least all of the liquid water from) a sulfamate-stabilized aqueous concentrate of active bromine of Group III) above.
  • a preferred solid-state microbiocidal composition of this type is formed by dewatering an aqueous biocide composition comprising water having in solution therein an active bromine content derived from (i) bromine chloride or bromine chloride and bromine, with or without conjoint use of chlorine, of at least 50,000 ppm (wt/wt) and preferably at least 100,000 ppm (wt/wt), and (ii) overbased alkali metal salt of sulfamic acid, wherein the relative proportions of (i) and (ii) are such that the atom ratio of nitrogen to active bromine is greater than 0.93, and wherein the pH of the composition is greater than 7, e.g., in the range of about 12 to 14.
  • a concentrated liquid biocide composition which comprises an aqueous solution of active bromine formed from (a) bromine, bromine chloride or a mixture of bromine chloride and bromine with (b) alkali metal salt of sulfamic acid and/or sulfamic acid, alkali metal base and water, or an aqueous solution of alkali metal salt of sulfamic acid formed from (1) alkali metal salt of sulfamic acid and/or sulfamic acid, (2) alkali metal base and (3) water, such aqueous solution of active bromine having a pH of at least about 7, and wherein the amounts of (a) and (b) are such that (i) the content of active bromine in the aqueous solution of active bromine is above about 160,000 ppm (wt/wt) (ii) the atom ratio of nitrogen to active bromine from (a) and (b) is greater than 1 when bromine
  • a process of forming a solid state bromine-containing biocidal composition comprises removing the water from an aqueous solution or slurry of a product formed in water from (A) (i) bromine, (ii) bromine chloride, (iii) a mixture of bromine chloride and bromine, (iv) bromine and chlorine in a Br2 to CI2 molar ratio of at least about 1 , or (v) bromine chloride, bromine, and chlorine in proportions such that the total Br2 to CI2 molar ratio is at least about 1 ; and (B) (i) alkali metal salt of sulfamic acid and/or sulfamic acid, and (ii) alkali metal base, wherein such aqueous solution or slurry has a pH of at least 7 and an atom ratio of nitrogen to active bromine from (A) and (B) of greater than 0.93.
  • a microbiocidally effective amount of at least one particular component is selected from at least one of the Groups designated as Groups I), II), III), and IV) and is dissolved in water.
  • the microbiocidally effective amount can vary depending upon various factors such as the identity of the particular component that is selected from Groups I), II), III), and IV), the amount and type of pathogen to be controlled, and the characteristics of the particular fruit or vegetable.
  • a microbiocidally effective amount of an antimicrobial composition of Groups I), II), III), and/or IV) is that which, upon addition to water, provides less than 100 ppm of active bromine, preferably in the range of 0.01 to 75 ppm (wt/wt) of active bromine, and more preferably, in the range of 0.01 to 50 ppm (wt/wt) in the resultant aqueous solution.
  • the aqueous microbiocidal composition applied to the fruit or vegetable is an aqueous microbiocidal composition that is stabilized against ultraviolet light-induced degradation by inclusion in the composition of at least one ultraviolet light stabilizer.
  • the ultraviolet light stabilizer(s) used in the microbiocidal compositions is/are selected from (i) ascorbic acid, (ii) dehydroascorbic acid, (iii) an edible water-soluble salt or ester of ascorbic acid, (iv) an edible water-soluble salt or ester of dehydroascorbic acid, or (v) a mixture of any two or more of (i) through (iv).
  • the term "edible” denotes that the substance is non-toxic and thus can be ingested by humans and the term “water-soluble” denotes that the salt or ester can be dissolved in water in an amount sufficient to achieve at least the minimum proportions relative to component (A) as set forth hereinafter under the heading "Proportions of Ultraviolet Light Stabilizer(s) Used.”
  • the aqueous microbiocidal compositions with which the ultraviolet light stabilizer(s) have been blended are characterized by having increased resistance against formation of bromate ion during exposure of the compositions to ultraviolet radiation.
  • the preferred ultraviolet light stabilizer(s) is/are ascorbic acid, especially L- ascorbic acid and its edible water-soluble salts and esters.
  • Non-limiting examples of suitable salts of ascorbic acid or of dehydroascorbic acid include metal salts such as sodium ascorbate, potassium ascorbate, calcium ascorbate, magnesium ascorbate, zinc ascorbate and also quaternary ammonium ascorbate salts and the corresponding salts of dehydroascorbic acid.
  • Esters of ascorbic acid, such as L- ascorbic acid, or of dehydroascorbic acid can be formed with organic or inorganic acids.
  • Non-limiting examples of suitable esters include L-ascorbic acid 2-0-sulfate, L-ascorbic acid 2-0-phosphate, L-ascorbic acid 3-0-phosphate, L-ascorbic acid 6-hexadecanoate, L- ascorbic acid monostyrate, L-ascorbic acid dipalmitate, and the like.
  • Alcoholic esters of ascorbic acid may also be used such as ethyl ascorbate, propyl ascorbate, isopropyl ascorbate, glyceryl ascorbate, and analogous alcoholic esters.
  • the ascorbic acid (Vitamin C) or compound having Vitamin C activity can be utilized in combination with at least one compound selected from the group consisting of the aldono-lactones of L-threonic acid, L- xylonic acid, L-lyxonic acid, and the edible salts of L-threonic acid, L-xylonic acid, and L- lyxonic acids. See in this connection U.S. Pat. Nos. 4,822,816; 4,968,716 and 5,070,085. Proportions of Ultraviolet Light Stabilizer(s) Used
  • the ultraviolet light stabilizer(s) is/are employed in an ultraviolet light- degradation inhibiting amount of up to about 1 part by weight of ultraviolet light stabilizer(s) per part by weight of bromine in the selected microbiocidal component with which it is associated.
  • at least one solid state microbiocidal compound of Group I e.g., l,3-dibromo-5,5-dimethylhydantoin or N,N'-bromochloro-5,5- dimethylhydantoin
  • at least one solid-state microbiocidal composition of Group IV e.g., a dewatered concentrated aqueous biocide composition formed by removing the
  • the proportion of the ultraviolet light stabilizer(s) is based on the weight of bromine in the solid-state microbiocidal compound or composition.
  • a liquid component from among the particular components of Group II) or Group III e.g., an aqueous solution or slurry of a solid-state microbiocidal compound having at least one bromine atom in the molecule of Group II), such as an aqueous solution of 1, 3 -dibromo- 5, 5 -dimethylhydantoin or of N,N'- bromochloro- 5, 5 -dimethylhydantoin, or a liquid Group III) concentrated aqueous
  • the aqueous microbiocidal composition applied to the fruit or vegetable contains a microbiocidally-effective amount of at least one aqueous antimicrobial composition selected from the individual members of Groups I), II), III), and/or IV) and an ultraviolet light degradation-inhibiting amount of up to about one part by weight of ultraviolet light stabilizer(s) per part by weight of active bromine in the selected microbiocidal composition.
  • the solid-state components used in forming the ultraviolet light- stabilized aqueous microbiocidal compositions that are applied to the fruit or vegetable are made from at least one particular component selected from at least one of the groups of A) and at least one of the ultraviolet light stabilizers of B) in a weight ratio in the range of about 0.25 part by weight of component B) per each part by weight of bromine in component A) to about 1 part by weight of component B) per each part by weight of bromine in component A).
  • the liquid-state components used in forming the ultraviolet light-stabilized aqueous microbiocidal compositions that are applied to the fruit or vegetable are formed from components A) and B) in a weight ratio in the range of about 0.25 part by weight of component B) per each part by weight of active bromine in component A) to about 1 part by weight of component B) per each part by weight of active bromine in component A).
  • a solid-state preformed mixture of components A) and B) can be added to or mixed with water or the solid forms of components A) and B) can be added to or mixed with water as separate ingredients in solid form.
  • the preformed solid-state blends of components A) and B) is preferred as it simplifies the blending operation and reduces the opportunity for blending errors.
  • the preformed aqueous concentrated solutions or slurries of components A) and B) are typically diluted in at least one step with sufficient water to form an ultraviolet light-stabilized microbiocidal aqueous composition which is applied to the fruit or vegetable.
  • other methods can be used when making up an ultraviolet light- stabilized microbiocidal composition for such use.
  • both a preformed aqueous concentrated solution or slurry of components A) and B) and more water can be added to an initial quantity of water or liquid-state mixture of particular liquid-state component selected from Groups II) and/or III) of A) and both a preformed aqueous concentrated solution or slurry of components A) and B) and a solid-state microbiocidal compound or composition from A) can be added to the water.
  • active bromine refers to all bromine- containing species that are capable of biocidal activity. It is generally accepted in the art that all of the bromine in the +1 oxidation state is biocidally active and is thus included in the term "active bromine”.
  • bromine, bromine chloride, hypobromous acid, hypobromite ion, hydrogen tribromide, tribromide ion, and organo-N- brominated compounds have bromine in the +1 oxidation state.
  • a typical starch-iodine titration to determine active bromine is carried out as follows: A magnetic stirrer and 50 milliliters of glacial acetic acid are placed in an iodine flask. The sample (usually about 0.2-0.5g) for which the active bromine is to be determined is weighed and added to the flask containing the acetic acid. Water (50 milliliters) and aqueous potassium iodide (15% (wt/wt); 25 milliliters) are then added to the flask. The flask is stoppered using a water seal.
  • the solution is then stirred for fifteen minutes, after which the flask is unstoppered and the stopper and seal area are rinsed into the flask with water.
  • An automatic buret (Metrohm Limited) is filled with 0.1 normal sodium thiosulfate.
  • the solution in the iodine flask is titrated with the 0.1 normal sodium thiosulfate; when a faint yellow color is observed, one milliliter of a 1 wt% starch solution in water is added, changing the color of the solution in the flask from faint yellow to blue. Titration with sodium thiosulfate continues until the blue color disappears.
  • the amount of active bromine is calculated using the weight of the sample and the volume of sodium thiosulfate solution titrated. Thus, the amount of active bromine in a composition of this invention, regardless of actual chemical form, can be determined by use of this method.
  • Another standard method for determining active bromine is commonly known as the DPD test procedure. This method is well suited for determining very small amounts of active bromine in aqueous systems. The standard DPD test for determination of low levels of active halogen is based on classical test procedures devised by Palin in 1974. See A. T.
  • Palin "Analytical Control of Water Disinfection With Special Reference to Differential DPD Methods For Chlorine, Chlorine Dioxide, Bromine, Iodine and Ozone", J. Inst. Water Eng., 1974, 28, 139. While there are various modernized versions of the Palin procedures, the recommended version of the test is fully described in Hach Water Analysis Handbook, 3rd edition, copyright 1997.
  • total chlorine ⁇ i.e., active chlorine
  • Method 8167 appearing on page 379.
  • the “total chlorine” test involves introducing to the dilute water sample containing active halogen, a powder comprising DPD indicator powder, ⁇ i.e., N,N'- diethyldiphenylenediamine), KI, and a buffer.
  • the active halogen species present react(s) with KI to yield iodine species which turn the DPD indicator to red/pink.
  • the intensity of the coloration depends upon the concentration of "total chlorine” species ⁇ i.e., active chlorine" present in the sample.
  • Hach Method 8167 for testing the amount of species present in the water sample which respond to the "total chlorine” test involves use of the Hach Model DR 2010 colorimeter. The stored program number for chlorine determinations is recalled by keying in "80" on the keyboard, followed by setting the absorbance wavelength to 530 nm by rotating the dial on the side of the instrument. Two identical sample cells are filled to the 10 mL mark with the water under investigation. One of the cells is arbitrarily chosen to be the blank. To the second cell, the contents of a DPD Total Chlorine Powder Pillow are added.
  • the SHIFT TIMER keys are depressed to commence a three minute reaction time. After three minutes the instrument beeps to signal the reaction is complete. Using the 10 mL cell riser, the blank sample cell is admitted to the sample compartment of the Hach Model DR 2010, and the shield is closed to prevent stray light effects. Then the ZERO key is depressed. After a few seconds, the display registers 0.00 mg/L Cl 2 .
  • the blank sample cell used to zero the instrument is removed from the cell compartment of the Hach Model DR 2010 and replaced with the test sample to which the DPD "total chlorine" test reagent was added.
  • the light shield is then closed as was done for the blank, and the READ key is depressed.
  • the result, in mg/L Cl 2 is shown on the display within a few seconds. This is the "total chlorine" level of the water sample under investigation. By multiplying this value by 2.25, the level of active bromine in the water sample is provided.
  • aqueous solution containing a microbiocidally-effective amount of a stabilized aqueous antimicrobial composition used pursuant to this invention can be immersed in a tank containing such aqueous solution, or the fruit or vegetable can be subjected to one or more sprays or mists of such aqueous solution.
  • the spray or mist can be applied by use of hand-held sprays or misting devices.
  • the sprays or mists can be applied from nozzles or misting devices disposed within spray or misting cabinets or zones into or through which the fruit or vegetable is conveyed as on a conveyor belt or other automated conveyor system.
  • a microbiocidally-effective amount of stabilized aqueous antimicrobial composition can be applied to the unharvested fruit or vegetable before the fruit or vegetable is/are removed from the field or orchard.
  • a spray of the composition can be applied to the vegetables while in the field and the fruit while on the trees.
  • the upper portion of the tree can be enveloped in a plastic film under which a fine spray, mist, or fog of the composition can be applied to the upper portion of the tree including the fruit.
  • the fruit or vegetable is then washed with water in order to thoroughly wash away the microbiocidal composition from the fruit or vegetable.
  • the time period between the application of the aqueous microbiocidal solution and the commencement of the water washing can vary, depending upon such factors as the identity of the microbiocide used in forming the aqueous microbiocidal solution, the concentration of the aqueous microbiocide in the aqueous microbiocidal solution used, and the nature and content of microbes, bacteria, fungus, yeast, mold, or other pathogens present or likely to be present on the fruit or vegetable.
  • the aqueous microbiocidal solution should remain in contact with the fruit or vegetable for a period in the range of about 10 seconds to about 30 minutes, and preferably in the range of about 30 seconds to about 5 minutes. Promptly thereafter the thorough water washing should be initiated.
  • a suitable non-toxic surface active agent surfactant, detergent, etc.
  • surfactant, detergent, etc. can be used in the washing operations to enhance the cleansing activity of the water wash.
  • the fruit or vegetable should be thoroughly washed with pure water.
  • Edible Fruits or Vegetables denotes any harvested or unharvested edible uncooked fruit or vegetable that is grown for consumption by humans.
  • edible fruits include plums, apricots, peaches, apples, oranges, lemons, limes, tangerines, grapefruit, bananas, pears, cherries, grapes, tomatoes, strawberries, cranberries, blueberries, blackberries, raspberries, gooseberries, figs, pineapple, watermelon, pumpkin, cantaloupe, mango, papaya, peanuts, walnuts, pecans, almonds, cashew nuts, prunes, raisins, dried figs, dried apricots, dried pineapple, dried cranberries, dried apples, and dried bananas, among others.
  • edible vegetables include potatoes, onions, green onions, shallots, garlic, carrots, turnips, beets, parsnips, radishes, rutabaga, celery, mushrooms, corn, okra, spinach, cabbage, kale, lettuce, broccoli, cauliflower, string beans, peas, cucumbers, squash, zucchini, among others.
  • This invention is deemed especially effective for use in microbiocidal treatment of leafy vegetables such as, for example, white cabbage, red cabbage, kale, iceberg lettuce, romaine lettuce, spinach, mustard greens, collard greens, watercress, dandelion, and leafy vegetables used as seasonings such as bay leaves, mint, thyme, basil, and oregano.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Storage Of Fruits Or Vegetables (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
PCT/US2008/050901 2007-01-12 2008-01-11 Microbiocidal treatment of edible fruits and vegetables Ceased WO2008089089A2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US12/517,646 US20100035950A1 (en) 2007-01-12 2008-01-11 Microbiocidal Treatment Of Edible Fruits And Vegetables
BRPI0806247-1A BRPI0806247B1 (pt) 2007-01-12 2008-01-11 Método para controlar a contaminação por bactéria, levedura e/ou mofo de pelo menos uma fruta ou um vegetal
JP2009545711A JP5337710B2 (ja) 2007-01-12 2008-01-11 食用の果物および野菜の殺微生物処理
CN2008800020421A CN101578048B (zh) 2007-01-12 2008-01-11 可食用的水果和蔬菜的杀微生物处理
US13/739,087 US9629376B2 (en) 2007-01-12 2013-01-11 Microbiocidal treatment of edible fruits and vegetables

Applications Claiming Priority (2)

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US88463307P 2007-01-12 2007-01-12
US60/884,633 2007-01-12

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US12/517,646 A-371-Of-International US20100035950A1 (en) 2007-01-12 2008-01-11 Microbiocidal Treatment Of Edible Fruits And Vegetables
US13/739,087 Continuation-In-Part US9629376B2 (en) 2007-01-12 2013-01-11 Microbiocidal treatment of edible fruits and vegetables

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WO2008089089A3 WO2008089089A3 (en) 2008-10-02

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US20100035950A1 (en) 2010-02-11
BRPI0806247A2 (pt) 2011-09-06
CN101578048A (zh) 2009-11-11
BRPI0806247B1 (pt) 2021-03-23
PE20081321A1 (es) 2008-11-01
AR064779A1 (es) 2009-04-22
JP2010515759A (ja) 2010-05-13
JP5337710B2 (ja) 2013-11-06
CL2008000074A1 (es) 2008-07-18
WO2008089089A3 (en) 2008-10-02
CN101578048B (zh) 2013-07-03

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