WO2004045655A2

WO2004045655A2 - Cleaning methods using chlorine dioxine solutions

Info

Publication number: WO2004045655A2
Application number: PCT/US2003/036492
Authority: WO
Inventors: Richard A. Hamilton; Gary A. O'neill; John J. Warner
Original assignee: Selective Micro Technologies, Llc
Priority date: 2002-11-14
Filing date: 2003-11-14
Publication date: 2004-06-03
Also published as: WO2004045655A3; AU2003290924A1; AU2003295499A1; AU2003295499A8; AU2003290924A8; WO2004045654A2; WO2004045654A3

Abstract

Disclosed are methods for cleaning that include exposing a target object, e.g., microelectronic equipment, water systems and prosthetics, to chlorine dioxide solutions. Also disclosed are kits and dispensers for practicing the methods of the invention.

Description

METHODS OF USING CHLORINE DIOXIDE SOLUTIONS

Related Applications

This application claims the benefit of U.S. Provisional Application Nos. 60/426,630, filed November 14, 2002 and 60/449,245, filed February 20, 2003, which applications are incorporated herein by this reference.

Field of The Invention

The present invention relates generally to methods of using chlorine dioxide solutions. In particular, the present invention relates to novel uses of chlorine dioxide solutions.

Background

The utility of chlorine dioxide for controlling, killing or preventing microbiological contamination (e.g., bacteria, fungi, viruses, mold spores, algae and protozoa); retarding, preventing, or controlling biochemical decomposition; controlling respiration, deodorizing and/or retarding and preventing chemotaxis to name a few, is known.

One disadvantage of the prior art in situ methods for generating chlorine dioxide solution generally is that unsatisfactory levels of by-products or reactants remain as a residue and the resulting acidity of the solution. In situ mixing of an acid and chlorite salt leaves high levels of residuals and low pH. For example, in the case of chlorine dioxide gas, the byproduct, chlorite, leaves residues on food handling equipment and medical and dental surfaces. Human or food contact with such residues should be avoided or substantially minimized according to FDA and EPA regulations.

Detailed Description of the Invention

The present invention provides several novel approaches to uses of chlorine dioxide as described and claimed below. ClO solutions can be generated or produced from reactants in a variety of forms such as tablets, powders (e.g. , zeolites impregnated or otherwise incorporating reactants), liquids (e.g., liquid solutions of reactants), gels, gases, and devices such as those described in U.S. Utility Patent No. 6,607,696 "Apparatus and Method for Controlled Delivery of a Gas" by Hamilton et al, U.S. Utility Patent No. 6,602,466, same title, International Patent Publication No. WO 01/60750, same title, and International Patent Publication No. W0 03/051406, same title. The solutions can be aqueous, and can be liquid or gaseous. The solution could also be in gel form. The present invention also features novel approaches to uses of a pure chlorine dioxide solution. The term "pure solution" is meant to embody a chlorine dioxide solution in which residues such as chlorite, chlorate and/or acid reactants that lower the pH are significantly reduced as compared to conventional solutions. A comparison of a pure solution of the invention to conventional chlorine dioxide solutions is presented in Table II below. Preferably, the pure solution includes chlorite at a level of less than about 60 ppm, more preferably less than about 50 ppm, even more preferably less than about 40 ppm; and/or chlorate at a level of less than about 50 ppm, more preferably less than 40 ppm, even more preferably less than 30 ppm. In another preferred embodiment, the solution includes chlorite at a level of less than about 30 ppm and more preferably 20 ppm, and/or chlorate at a level of less than about 20 ppm, and more preferably 15 ppm. Preferably, the pure chlorine dioxide solution has a pH of greater than about 5, and more preferably greater than about 6, and most preferably a pH of about 6.5. The pure chlorine dioxide solutions are preferably aqueous solutions, and the aqueous solutions can be gaseous or liquid, or even in gel form. When in gaseous form, the solution preferably is a ClO₂ gas present over an aqueous solution such as a mist, vapor or fog. These preferred parameters and forms apply to all applications disclosed herein, although further preferred embodiments may additionally be provided and claimed.

An example of a pure solution of the invention is illustrated in Table I where for every 500 parts per million (ppm) of chloride dioxide (ClO₂) generated, the residue of Chlorite (ClO₂ ^") is about 11 ppm and Chloride (ClO ^") is about 9 ppm. Methods and devices for in situ generation of a pure chlorine dioxide solution in useful quantities with low residuals and neutral pH is described in U.S. Utility Patent No. 6,607,696 "Apparatus and Method for Controlled Delivery of a Gas" by Hamilton et al, U.S. Utility Patent No. 6,602,466, same title, and International Patent Publication No. WO 01/60750, same title, and international Patent Publication No. W0 03/051406, same title. Other devices capable of generating a relatively pure solution of chlorine dioxide may also be used in the applications described. As mentioned above, Table I outlines the differences in residual chlorite (ClO₂ ^"), chlorate (ClO₃ ^") and pH between conventional in situ chlorine dioxide solution generation devices and methods and the devices described in the Hamilton et al. patent application. All values are at the time of generation according to product instructions. Table I: Differences in Chlorine Dioxide Solution Purity

The aqueous solution of chlorine dioxide for each product was prepared according to the manufacturer's instructions and ClO₂ and ion concentrations were measured at the time of generation with a Hach DR 1890 spectrophotometer, Hach

10 (Loveland, CO) and a Lachat IC 1000, Lachat (Loveland, CO), respectively, with the exception of the Sterling Pulp Generator data, which was taken from the manufacturer's website. All values have been adjusted proportionally, for comparison purposes, to the generation of a 500 ppm solution of chlorine dioxide.

In many applications, the relatively high residual levels of chlorate and chlorite

15 and other species in the previous methods for in situ chlorine dioxide solution generation have the potential to cause significant deleterious effects. Conventional devices and methods of ClO₂ generation not only generate residuals, but also often increase the acidity of the solution which also can be disadvantageous. A summary of these effects is presented in Table II below.

20.

Table II: Deleterious Effects of Residuals and Acidity in Various Applications

Application Effect of Residuals Effect of Acidity

Dental Unit Water Lines Regulatory, Taste, Efficiency Corrosion Soft Drink Beverage Lines Regulatory, Taste, Efficiency Corrosion

Ice Machines Regulatory, Taste, Efficiency Corrosion

Coffee Makers & Dispensers Regulatory, Taste, Efficiency Corrosion

Laboratory Water Systems Regulatory, Efficiency Corrosion

Decontamination of Lab Waste Regulatory

Beer Taps & Lines Regulatory, Taste, Efficiency Corrosion

Glassware Sanitization Regulatory, Taste, Aesthetics

Dairy Processing Regulatory, Taste, Efficiency Corrosion

Chemistry, Hematology and Immunoassay Performance, Efficiency, Corrosion

Analyzers Regulatory

Post Harvest Vegetable Wash Regulatory, Taste, Aesthetics Aesthetics, Taste Application Effect of Residuals Effect of Acidity

Processed Food Sanitization Regulatory, Taste, Aesthetics Aesthetics, Taste

Beef, Poultry, Pork, Fish Carcass Wash Regulatory, Taste, Aesthetics Aesthetics, Taste

Ethylene Destruction Regulatory

Mushroom Growing Regulatory, Taste Aesthetics Aesthetics, Corrosion

Post Harvest Mushroom Sanitization Regulatory, Taste, Aesthetics Aesthetics, Corrosion

Veterinary Clinical Disinfection Regulatory Corrosion

Veterinary Deodorization Corrosion

Endodontics Regulatory Aesthetics,

Regulatory

Wound Irrigation and Disinfection Regulatory Aesthetics,

Regulatory

Wound Dressing Regulatory Aesthetics,

Regulatory

Endoscope Disinfection Regulatory Corrosion,

Aesthetics,

Regulatory

Immersion Sterilization Regulatory Corrosion Surface Disinfection Regulatory, Efficiency Corrosion Medical & Dental Equipment Disinfection Regulatory Efficiency, Corrosion, Aesthetics

Aesthetics

Greenhouse Irrigation Systems Regulatory, Efficiency Corrosion Decontamination Greenhouse Mister Systems Decontamination Regulatory, Efficiency Corrosion Greenhouse Tools and Trays Disinfection Regulatory, Efficiency Corrosion Greenhouse Surfaces and Floors Regulatory, Efficiency Corrosion Decontamination Greenhouse Cuttings Dip for Propagation Regulatory, Efficiency, Aesthetics Cut Flower Dip Regulatory, Aesthetics Cut Flower Ethylene Destruction Regulatory, Aesthetics Consumer Cut Flower Preservative Regulatory, Aesthetics Retail Floral Preservative Regulatory, Aesthetics Removal of Biofilm from Chillers Regulatory, Efficiency Corrosion Drinking Water Purification Regulatory, Taste, Efficiency Corrosion Marine Water Tanks & Lines Regulatory, Taste, Efficiency Corrosion Seawater Contact Surfaces Regulatory, Aesthetics Corrosion Industrial Mold Control & Removal Regulatory, Aesthetics Corrosion Domestic Mold Control and Removal Regulatory, Aesthetics Corrosion, Aesthetics Surface Disinfection in Hospitals, Clinics, Regulatory, Aesthetics Corrosion Dental Surface Disinfection in Restaurants Regulatory, Efficiency Corrosion Surface Disinfection in Homes Regulatory, Aesthetics Corrosion, Aesthetics Aircraft Water Line and Tank Decontamination Regulatory, Taste, Efficiency Corrosion,

Regulatory

Industrial Process Water Recovery and Regulatory, Efficiency, Corrosion, Purification Aesthetics Regulatory,

Efficiency

Water Storage Tanks Regulatory, Efficiency, Taste Taste, Corrosion Reverse Osmosis Membrane Decontamination Regulatory, Efficiency, Corrosion, Aesthetics

Aesthetics

Process Microfiltration Decontamination Regulatory, Efficiency, Corrosion, Aesthetics

Aesthetics

Domestic Bathroom Sanitization or Disinfection Efficiency, Aesthetics Corrosion, Aesthetics Home Heating System Decontamination or Regulatory, Efficiency, Corrosion, Aesthetics

Deodorization Aesthetics Humidifier Sanitization, Biofilm Prevention Regulatory, Efficiency, Corrosion, Aesthetics

Aesthetics

Hot Tub & Spa Decontamination and Water Regulatory, Efficiency, Corrosion, Aesthetics

Purifier Aesthetics Decorative Fountain Biofilm Prevention Regulatory, Efficiency, Corrosion, Aesthetics Application Effect of Residuals Effect of Acidity

Aesthetics

Pool and Spa DE/Sand Filter Decontamination Regulatory, Efficiency, Corrosion, Aesthetics

Aesthetics

Athlete's Foot Remedy Regulatory, Efficiency, Regulatory,

Aesthetics Efficiency

Brewing Equipment Cleaning and Sanitizing Regulatory, Taste, Efficiency, Efficiency, Corrosion,

Aesthetics Taste

Beer Keg, Bottle and Can Sanitizing Regulatory, Taste, Efficiency, Efficiency, Corrosion,

Aesthetics Taste

Beer Yeast Wash Regulatory, Taste, Efficiency Efficiency, Corrosion,

Taste

Wine Filter Press Sanitizing Regulatory, Taste, Efficiency Efficiency, Corrosion,

Taste

Wine Processing Equipment Sanitizing Regulatory, Taste, Efficiency Efficiency, Corrosion,

Taste

Wine Bottle and Cork Sanitizing Regulatory, Taste, Efficiency, Efficiency, Corrosion,

Aesthetics Taste

Microelectronics Manufacture Decontamination Regulatory, Efficiency Efficiency, Corrosion Biological Agent Destruction Regulatory, Efficiency Efficiency, Corrosion Dental Plaque Control Regulatory, Taste, Efficiency, Taste, Efficiency,

Aesthetics Aesthetics

Peridontal Disease Treatment Regulatory, Taste, Efficiency, Taste, Efficiency,

Aesthetics Aesthetics

Biocidal Hand Wash Regulatory, Taste, Efficiency, Efficiency, Aesthetics

Aesthetics

Effects Key:

Regulatory: Residuals or acidity levels may exceed a regulated (EPA, FDA, USDA, etc.) level

Taste: Residuals or acidity may adversely affect the taste food, water, beverages

Corrosion: Residuals or acidity may corrode or weaken materials used in the application

Aesthetics: Residuals or acidity adversely affect appearance, appeal

Performance: Residuals or acidity adversely affects the performance of the object

Efficiency: Residuals or acidity adversely affect the application, cost or performance of the chlorine dioxide application (e.g., wash-out time for post decontamination cleanings).

Until now, the need for pure solutions has not been met by conventional devices and methods for in situ generation. Table III includes a summary of some of the applications of the present invention, together with exemplary protocols for meeting the relevant cleaning requirements to the applicable industry by application of the methods of the invention.

Table III: Application Protocols

APPLICATION Concentration Contact Time METHOD (ppm)

Dental Unit Water Lines

Disinfection 50-100 10-20 min Fill lines with solution

Biofilm Removal 50-100 30 min - 8 hours Fill lines with solution APPLICATION Concentration Contact Time METHOD

Soft Drink Beverage Lines

Disinfection 50-100 10-20 min Fill and flush lines with solution

Biofilm Removal 50-100 30 min - 8 hours Fill lines with solution

Sanitization 5-10 1-5 min Fill and flush lines with solution

Ice Machines

Disinfection 50-100 10-20 min Flush lines and cabinet, spray

Biofilm Removal 50-100 30 min - 8 hours Fill lines and let stand in cabinet

Sanitization 5-10 1-5 min Flush lines and cabinet, spray

Deodorization 1-5 immediate Flush lines and cabinet, spray or continuous

Coffee Makers & Dispensers

Biofilm Removal 50-100 30 min - 8 hours Fill apparatus with solution

Sanitization 5-10 1-5 min Rinse apparatus with solution

Laboratory Water Systems 1-100 30 sec-continuous Continuous application or flush

Laboratory Water Tanks 50-100 15 min - 8 hrs soak and flush

Decontamination of Lab 1-500 30 sec-hours Immerse, flush

Waste

Beer Taps & Lines

Disinfection 50-100 10-20 min Fill and flush

Sanitization 5 1 min Fill and flush

Glassware Sanitization 5 ^• 30 sec-1 min Rinse in solution

Dairy Processing

Equipment Disinfection 50-100 10-20 min Rinse, wipe, spray

Equipment Sanitization 5 1 min Rinse, wipe, spray

Chemistry, Hematology and Immunoassay Analyzers

Decontamination 50-100 15-30 min Full lines & Tanks, Rinse

Sanitization, Prevent Biofilm 1-5 Continuous Through water system

Post Harvest Vegetable Wash 1-5 30 sec-5 min Rinse, dip

Processed Food Sanitization 5 30 sec-1 min Rinse, Dip, Spray

Beef, Poultry, Pork, Fish 2-10 30 sec -5 min Rinse, Spray, Dip

Carcass Wash

Ethylene Destruction 0.01-500 1-30 min Immerse, mix, spray, mist

Mushroom Growing

Misting 1-5 1 min-continuous Fill lines, mist

Algae and Biofilm Removal 5-100 1-30 min Spray, wipe, mop, flush

Equipment Sanitization or 5-100 1-30 min immerse, spray, flush, APPLICATION Concentration Contact Time METHOD

Disinfection wipe, mop

Post Harvest Mushroom 1-10 30sec-5 min Immerse, dip, spray, Sanitization rinse

Veterinary Clinical 50-100 10-20 min Spray, immerse, dip, Disinfection fumigate

Veterinary Deodorization .01-5 instantaneous spray, wipe, exposure

Endodontics 2-100 5 sec-30 min spray, wipe, irrigate

Wound Irrigation and 2-100 5sec-30 min Spray, wipe, irrigate Disinfection

Wound Dressing 2-100 5 sec-30 min spray, wipe, irrigate

Endoscope Disinfection 50-500 10 min-8 hrs spray, immerse

Immersion Sterilization 50-500 10 min-8 hrs immerse

Surface Disinfection 50-100 10-20 min spray, wipe, immerse

Medical & Dental Equipment 50-100 10-20 min spray, wipe, immerse Disinfection

Greenhouse Irrigation Systems 1-100 30 sec-continuous fill lines, mist, rinse Decontamination

Greenhouse Mister Systems 1-100 30 sec-continuous lines, mist, rinse Decontamination

Greenhouse Tools and Trays 5-100 10 min-4 hrs immerse, wipe, spray Disinfection

Greenhouse Surfaces and 5-100 10 min-8 hrs wipe, spray, mop, flood Floors Decontamination

Greenhouse Cuttings Dip for 5-40 30 sec-5 min immerse, spray, dip Propagation

Cut Flower Dip 2-40 1 sec -5 min immerse, spray, dip

Cut Flower Ethylene 0.01-5 30 sec-continuous spray, dip, continuous Destruction

Consumer Cut Flower 1-40 30 sec-continuous dip, immerse,¹ continuous Preservative

Retail Florist Preservative 1-40 30 sec-continuous dip, immerse, continuous

Removal of Biofilm from 2-200 30 min-continuous fill, rinse lines, tanks, Chillers continuous

Drinking Water Purification 2-10 10-30 min add to water, let stand

Marine Water Tanks & Lines

Sanitization 2-5 1 min-8 hrs rinse lines & tanks Biofilm Removal 50-200 1 min-8 hrs rinse lines & tanks APPLICATION Concentration Contact Time METHOD

Deodorization 0.1-5 1 min-continuous fill lines, tanks

Seawater Contact Surface 50-200 5 min- 2 hrs spray, wipe, rinse Decontamination

Industrial Mold Control & 0.1-100 10 min-8 hrs Spray, wipe, fumigate Removal

Domestic Mold Control and 0.1-100 10 min-8 hrs Spray, wipe, fumigate Removal

Surface Biocide in Hospitals, Clinics, Dental

Sanitization 2-10 30 sec-30 min spray, wipe, dip, immerse

Disinfection 50-100 10-20 min spray, wipe, dip, immerse

Surface Biocide in

Restaurants

Sanitization 2-10 30 sec-30 min spray, wipe, dip, immerse

Disinfection 50-100 10-20 min spray, wipe, dip, immerse

Antimicrobial 1-5 30 sec-30 min spray, wipe, dip, immerse

Surface Biocide in Homes

Disinfection 50-100 10-20 min spray, wipe, dip, immerse

Sanitization 2-10 30 sec-30 min spray, wipe, dip, immerse

Antimicrobial 1-5 30 sec-30 min spray, wipe, dip, immerse

Aircraft Water Line and Tank

Decontamination

Sanitization 2-5 1 min-8 hrs fill, rinse lines & tanks

Disinfection 50-100 15 min-1 hr fill lines, tanks, drain

Biofilm Removal 50-200 1 min-8 hrs fill, rinse lines & tanks

Deodorization 0.1-5 1 min-continuous fill lines, tanks

Industrial Process Water Recovery and Purification

Water Storage Tanks

Sanitization 2-5 1 min-8 hrs fill, rinse lines & tanks

Biofilm Removal 50-200 1 min-8 hrs fill, rinse lines & tanks

Deodorization 0.1-5 1 min-continuous fill lines, tanks

Reverse Osmosis Membrane 5-200 1 min-2 hrs Fill, circulate, rinse

Decontamination

Disinfection 50-200 10-30 min Fill, circulate, rinse

Sanitization 5-50 1-5 min Fill, circulate, rinse

Process Microfiltration 5-200 1 min-2 hrs Fill, circulate, rinse

Decontamination

Domestic Bathroom Sanitization or

Disinfection

Disinfection 50-100 10-20 min spray, wipe, dip, immerse

Sanitization 2-10 30 sec-30 min spray, wipe, dip, immerse

Antimicrobial 1-5 30 sec-30 min spray, wipe, dip, immerse

Home Heating System 1-100 30 sec-continuous add to tank, fill, rinse Decontamination and/or Deodorization APPLICATION Concentration Contact Time METHOD

Humidifier Sanitization, Biofilm 1-5 continuous add to tank, fill

Prevention

Hot Tub & Spa 1-200 1 min-continuous add to water or fill and

Decontamination and Water rinse

Purifier

Decorative Fountain Biofilm 1-5 continuous add to water

Prevention

Pool and Spa DE/Sand Filter 1-200 1 hr-continuous add to water or filter

Decontamination

Athlete's Foot Remedy 5-50 30 sec-30 min immerse, spray

Locker Room Floor 5-50 1-30 min Mop, spray

Decontamination

Brewing Equipment Cleaning 5-50 30 sec-1 hr spray, fill tanks & lines, and Sanitizing rinse,

Beer Keg, Bottle and Can 5-50 30 sec-5 min spray, immerse, rinse

Sanitizing

Beer Yeast Wash 1-50 30 sec-8 hrs immerse, spray

Wine Filter Press Sanitizing 2-50 30 sec-1 hr fill, spray, rinse

Wine Processing Equipment 2-50 30 sec-1 hr fill, spray, rinse Sanitizing

Wine Bottle and Cork 2-50 30 sec-1 hr fill, spray, rinse Sanitizing

Microelectronics Manufacture 1-100 30 sec-continuous spray, rinse, continuous, Decontamination soak

Biological Agent Destruction 5-500 30 sec-8 hrs spray, immerse, continuous

Dental Plaque Control 2-20 30 sec-5 min spray, irrigate, sponge soak

Peridontal Disease Treatment 2-20 30 sec-5 min spray, irrigate, sponge soak

Biocidal Hand Wash 2-100 30 sec-10 min wipe, immerse

For the purposes of the present invention, here and throughout, the terms "contacting," "delivering," and "administering" shall include methods of washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging and storing the targeted object in the ClO₂ solution. These procedures provide a means for cleaning the targeted objects of the present invention and all of the methods of the present invention can utilize any of these means and their variants. Cleaning is a general term that includes various levels of biocidal and antimicrobial activity. That is, any and all of the cleaning methods of the present invention can further mean, e.g., deodorizing, sanitizing, disinfecting, sterilizing, and removing and/or preventing biofilm growth or accumulation. Disinfecting generally involves killing pathogenic organisms in water, air, or on surfaces. Sterilizing generally involves the removal or destruction of all microorganisms, including pathogenic and other bacteria, vegetative forms, and spores.

The present invention includes the following novel approaches to the use of chlorine dioxide solutions.

Microelectronics One embodiment of the present invention features a method of cleaning microelectronic equipment that includes providing a ClO₂ solution and exposing the microelectronic equipment to the ClO₂ solution. A requirement of microelectronic processing is removal of particulate matter from the chip substrate, such particles include bacteria. Currently expensive and large systems, such as ozone injection systems, are used to control bacteria and other particulates. This embodiment contemplates, e.g., bacterial removal and control, particularly bacterial control at the stations where chips are manufactured (e.g., a tool station). This embodiment also contemplates the removal and control of other microbiological organisms.

Manufacturers and users of microelectronics will use the present embodiment to clean their microelectronic equipment. Possible ways to practice the present embodiment include washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging or storing the equipment in the ClO₂ solution. The solution can be in the form of a pure solution, aqueous solution, liquid or a gas, as well as all other forms discussed throughout this application. Preferably, the ClO₂ solution is a pure solution.

Prosthetics and Other Medical Devices

Concerning prosthetics, a preferred embodiment of the present invention focuses on a method of cleaning prosthetics by providing a ClO₂ solution, and contacting the prosthetic equipment with the solution. The present invention specifically contemplates joints and endodontics. Other medical devices can be cleaned in the same manner. The medical devices can be any medical devices such as orthotics, stents, catheters, endoscopes, resectors, clamps, sutures, scalpels, implants, pacemakers, implanted pharmaceutical delivery devices, e.g., insulin pumps and pick lines. These prosthetics and other medical devices can be cleaned, e.g., by washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging or storing the device in the ClO₂ solution. The solution preferably is a pure ClO₂ solution, and can be in any form, e.g., a liquid, a gas, or mist.

Wounds

One currently preferred embodiment is a method of irrigating wounds by providing a ClO₂ solution and administering the solution to the wounded area.

Administration of the solution can be by washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing or sparging the wound. The wound can be a result of any number of causes, such as an accident or an invasive operation. As in the aforementioned embodiments, the solution can be in a variety of forms including an aqueous solution, and in the form of a gas, a gel, or a liquid. Preferably, the ClO₂ solution is a pure solution.

Body wash

Another embodiment of the present invention includes a method of cleaning the body. The method includes providing a ClO₂ solution, and contacting the body with the ClO₂ solution. The method is particularly useful for hand and arm cleaning in hospital environments, food service environments, dental environments, and laboratory environments, where frequent hand washing is required and conventional cleaners damage the skin. The method is also useful for cleaning and preparing body parts prior to the performance of a medical procedure, e.g. , surgical scrubs. The cleaning can include deodorizing, disinfecting and sterilization. Washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, or sparging with or in the ClO₂ solution is contemplated to be within the scope of this embodiment. The ClO₂ solution can be in a pure solution, and can be gaseous or liquid. Preferably, the ClO₂ solution is a pure solution. The solution can further include soap, detergent, surfactant, or other cleansing agents; the soap can be added to a ClO₂ solution or means of generating a ClO solution can be added to the soap to generate ClO₂ in situ. In a preferred embodiment, the solution is provided in a dispenser at the site of cleansing, e.g., in a hospital wash area. For use in remote locations, the solution can be provided via a kit as described below.

Aquariums Another embodiment of the present invention includes a method of cleaning aquarium equipment that includes producing a ClO₂ solution, and contacting a surface with the ClO₂ solution. The equipment includes fish tanks, water regulation systems, filters, thermometers, pumps, tank covers, and the like. The equipment can further include an aquatic environment, and the cleaning can remove biofilm and/or algae from the aquatic environment. The cleaning can include deodorizing, disinfecting and sterilization. Washing, dipping, flushing, spraying, storing, and immersion in the ClO₂ solution are contemplated to be within the scope of this embodiment. The ClO₂ solution can be in a pure solution, and can be gaseous or liquid. Preferably, the ClO₂ solution is pure.

In another embodiment, the present invention is directed to treating or preventing a fish disease by providing a ClO₂ solution, and administering the ClO₂ solution to an aquatic environment which includes a fish. The fish disease can be, e.g., a bacterial infection, a fungus, or a parasite. Exemplary fish diseases include ich, fin rot, saprolegnia, and chilodonella. Preferably the ClO solution is a pure solution, and can be gaseous or liquid.

Equipment Another embodiment of the present features a method of cleaning equipment that includes providing a ClO₂ solution, and exposing the equipment to the solution. In one exemplary embodiment, the equipment is a medical device or apparatus. In another embodiment, the medical device includes a fluid line. As discussed herein, fluid lines can range from beer taps, dairy equipment, water lines, to blood analyzers and dialysis machine lines. In another exemplary embodiment, the equipment is pharmaceutical processing equipment, e.g., homogenizers, pressure vessels, stills or storage tanks. In another exemplary embodiment, the equipment is hospital equipment. For example, an endoscope can be sterilized by immersion into the solution. Also, wound cleaning as previously described can be included in hospital usage by combining the disinfecting of certain hospital equipment, such as sutures, with the irrigation of wounds. In still a further embodiment, equipment is clinical equipment. This clinical equipment include a variety of devices including, but not limited to, analyzing equipment, gas phase analyzers, and gas phase decontamination equipment and methods.

In a preferred embodiment, the solution consists of a pure ClO₂ solution in aqueous form but may vary in form to a gas mixture or mist. The delivery of the ClO₂ solution is by means of washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging or storing the equipment in the ClO₂ solution. As with the previous embodiments, this procedure provides a means for disinfecting, sterilizing, aesthetic cleaning, and deodorizing the equipment.

Water Systems

Another embodiment of the present invention includes a method of cleaning or decontaminating water systems that includes, providing a ClO₂ solution and administering the solution to a water system. This process can be applied to water systems that include, e.g., storage tanks, and reverse osmosis (RO) decontamination. For RO systems, the ClO₂ solutions of the invention are particularly advantageous because, when added to the feed side of the membrane, the ClO₂ gas reduces or eliminates biofilm, not only on the feed side of the membrane, but also on the product side. This is primarily because the gas does not hydrolyze in water, and has a neutral charge, thus allowing it to pass through the membrane. This process can also be applied to deionization (DI) systems, which function in a manner similar to that of RO systems. Further water systems can be directed to bacterial control, maintenance and use of process micro-filtration and ultra-filtration (UF). The solution can be administered the techniques described throughout this application. The invention includes washing, wiping, bathing, spraying, flushing, sparging or storing the water system, or dipping, soaking or immersing components of the water system in the ClO₂ solution.

Components of the water system include, but are not limited to, membranes, tubes and other parts. Preferably, the solution is pure ClO₂, and may be administered in liquid or gaseous form.

Luns Disease

The present invention is also directed to a method for treating a lung disease or disorder. The method includes providing a ClO₂ solution, and contacting the lungs with the ClO₂ solution. Preferably, the ClO₂ solution is provided in the form of a spray, a mist, a vapor or a steam using, e.g., a vaporizer, an atomizer or an inhaler. The ClO₂ solution is preferably inhaled in order to contact the lungs. The ClO₂ solution can be a pure ClO₂ solution, and can be used to kill, e.g., bacteria or other microorganisms in the lungs. Preferably, the solution is a pure ClO₂ solution. In a preferred embodiment, the ClO solution is used to treat biofilms in the lungs, e.g., cyctic fibrosis. Biofilms are difficult to treat with antibiotics, and it is believed that ClO₂ will be effective. In another embodiment, the method is employed to treat lung bacteria, such as Streptococcus pneumoniαe, lung viruses, lung mycoplasma, lung fungus (e.g., Pneumocystis cαrinii pneumonia), and other organisms such as Rickettsia, which causes Rocky Mountain spotted fever, a fever, typhus and psittacosis.

Water Purification

The present invention includes a novel approach for water purification. The present invention uses a unique method of a delivery system where the water is purified by the delivery of chlorine dioxide gas in an aqueous solution and adding this solution to body of water in need of purification. In another embodiment, the ClO gas is generated in the body of water.

One embodiment includes the purification of water in waterlines and the water with the lines. Waterlines are systems which are meant to transport both potable and non potable water from the supply to another location for use. Waterlines contemplated by the present invention include, but are not limited to, coffee machine water lines, boat or marine waterlines, hotel water lines, recreational vehicle waterlines, aviation water lines, hospital waterlines, beverage machine waterlines, ice machine waterlines, pot filler water lines. Another embodiment of the invention features the purification of water disposed in a storage tank. Storage tanks which could utilize the present invention include, but are not limited to, boat storage tanks, recreational vehicle storage tanks, camping storage tanks, laboratory storage tanks, municipal reservoirs, military storage tanks, floor storage tanks, airplane storage tanks, aquatic storage tanks, and fish storage tanks. The present invention features the cleaning of waterlines by providing an aqueous chlorine dioxide solution which when used with a targeted surface disinfects, sanitizes, decontaminates, deodorizes, and removes and/or prevents biofilm growth or accumulation. The chlorine dioxide is preferably in a pure solution form. Dental Equipment

In another aspect of the present invention is a method for cleaning dental equipment by providing a ClO₂ solution and exposing the dental equipment to the ClO₂ solution. Preferably, the ClO₂ solution is in pure solution form. For the purposes of the present embodiment, dental equipment includes, but is not limited to, dental water lines, dental tools and other various equipment used in dental procedures. The ClO₂ solution may be introduced to the dental equipment by washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging or storing in solution for the purposes of disinfecting, deodorizing, sterilizing, and sanitizing.

Beverase In yet another embodiment, the present invention can be used in the cleaning of beverage equipment by providing a ClO₂ solution, and contacting the beverage lines with the solution. The term beverage includes carbonated (e.g., soft drinks), uncarbonated, frozen, unfrozen, alcoholic (e.g., beer), and non-alcoholic drinks meant for consumption. The term beverage equipment pertains to all apparatus used in the production, delivery and dispensing of beverages, such as beverage lines, dispensing taps, storage canisters, and dispensing stands. Furthermore, this invention may utilize a pure solution of chlorine dioxide and could be administered in an aqueous solution, or in gas form. Preferably, the solution is a pure ClO₂ solution. In another embodiment of beverage equipment cleaning, the ClO solution may be introduced to the beverage equipment by washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging or storing in solution for the purposes of disinfecting, sanitizing, sterilizing, and/or deodorizing.

Ice Machines

In another aspect, the present invention features a method of cleaning ice machine equipment by preparing a ClO₂ solution, and administering this solution to the ice machine equipment. Ice machine equipment includes water lines, ice storage containers, and other devices incorporated into ice making apparatus. The ice machine equipment is treated with a ClO₂ solution, preferably a pure ClO₂ solution. This solution can be aqueous and imparted to the equipment by means of washing, wiping, immersing, dipping, bathing, sparging, soaking, spraying, storing in solution, or flushing. This procedure provides disinfecting, sterilizing, sanitizing, aesthetic cleaning, and deodorizing.

The present invention features the cleaning of ice machine equipment by providing an aqueous chlorine dioxide solution which when used disinfects, sanitizes, decontaminates, deodorizes, and removes and/or prevents biofilm growth or accumulation. The chlorine dioxide may be in a pure solution form.

Coffee and Espresso Equipment

In yet another preferred embodiment, the present invention includes a method of cleaning coffee equipment by preparing a ClO₂ solution, and contacting the coffee equipment with the solution. Additionally or alternatively, the ClO₂ can be generated in a body of water inside the coffee equipment. The term coffee equipment is meant to encompass various forms of coffee making apparatus such as water lines, coffee dispensers, water reservoirs or water storage containers, espresso-making equipment. One preferred embodiment further calls for the ClO solution to be a pure solution which can be in an aqueous or a gas form. The ClO solution is applied to the coffee equipment by methods embracing washing, wiping, immersing, dipping, bathing, sparging, soaking, flushing, storing equipment in solution, and spraying the equipment with the ClO₂ solution. This procedure provides means for disinfecting, sterilizing, sanitizing, aesthetic cleaning, and deodorizing the coffee equipment.

Pot Fillers

In yet another preferred embodiment, the present invention includes a method of cleaning pot fillers, including water lines and reservoirs by providing a ClO₂ solution, and contacting the pot filler with the solution. For the purposes of this invention, a pot filler may include, among other components, a fluid line, a water reservoir and/or a water storage container. Preferably, the ClO solution is a pure solution, which can be an aqueous solution, liquid or gaseous. The ClO₂ solution is applied to the pot filler by methods embracing wiping, immersing, dipping, bathing, sparging, washing, soaking, flushing, storing equipment in solution, and spraying with the equipment with the ClO₂ solution. This procedure provides means for disinfecting, sterilizing, sanitizing, aesthetic cleaning, and deodorizing the pot filler. Laboratory

In yet a further embodiment, the present invention features a method of cleaning laboratory equipment by providing a ClO₂ solution, and contacting the laboratory equipment with the solution. The term "laboratory equipment" is meant to encompass equipment used in a laboratory, such as water lines, water systems and water reservoirs or water storage containers. Laboratory equipment can further include any equipment, glassware, instrument, water purification system, purification apparatus, or other apparatus used in a laboratory in which a surface is need of disinfecting, sanitizing, deodorizing or cleaning. Laboratory equipment includes, e.g., scalpels, tongs, beakers, pipettes, petri dishes, and test tubes. The ClO₂ solution is preferably a pure solution in an aqueous solution but could take the form of a liquid, gas or mist. The ClO₂ solution can be applied to the laboratory equipment by methods of wiping, soaking, bathing, flushing, sparging, washing, spraying, dipping, immersing, and storing equipment in a solution. This application provides a means of disinfecting, sterilizing, aesthetic cleaning, and deodorizing the laboratory equipment.

A further embodiment o the present invention is directed to a method of cleaning laboratory equipment which is used in the decontamination of laboratory waste. Again, the solution is preferably an aqueous pure ClO₂ solution. The ClO₂ solution can be applied to the laboratory equipment by methods of wiping, bathing, washing, spraying, soaking, sparging, flushing, soaking, dipping, immersing, and storing equipment in a solution. This procedure provides a means for disinfecting, sterilizing, sanitizing, aesthetic cleaning, and deodorizing the laboratory equipment.

Food Industry In another aspect, the present invention features a method of cleaning a food product surface including the steps of providing a pure ClO aqueous solution, and contacting the food product with the ClO₂ aqueous solution. Preferably, the pure solution includes chlorite at a level of less than about 60 ppm, more preferably less than about 50 ppm, even more preferably less than about 40 ppm; and/or chlorate at a level of less than about 50 ppm, more preferably less than 40 ppm, even more preferably less than 30 ppm. In another preferred embodiment, the solution includes chlorite at a level of less than about 30 ppm and more preferably 20 ppm; and/or chlorate at a level of less than about 20 ppm, and more preferably 15 ppm. Additionally, the pH of the ClO₂ solution is preferably above about 5.5. This embodiment provides a method for disinfecting a food product surface. A few of the food products contemplated by this invention are animal or fish carcasses, pre- and post-harvest fruits, vegetables, nuts and herbs, processed foods, and pre-harvest mushrooms, post-harvest mushrooms. In some embodiments, the cleaning is directed to the treatment of harmful bacteria, e.g., E. coli and/or salmonella. In other embodiments, the cleaning is directed to ethylene destruction.

Cleaning can further mean disinfecting, sterilizing and/or sanitizing. Methods of cleaning carcasses with a pure chlorine dioxide solution in accordance with the present invention can further include aspects of conventional carcass washing methods, such as those described in United States Patent No. 6,063, 425 by Kross et al. and United States Patent No. 6,245,294 by Goldberg et al. In conventional carcass washes, the solutions used require extra washes to remove residuals, e.g., chlorates and chlorites. The presence of such residuals not only may violate food quality regulations, but also can change the color and/or taste of the food products. Accordingly, a pure ClO₂ aqueous solution is preferred to avoid the added expense of removal of residuals, to minimize the risk of not passing health and safety regulations, and to preserve taste and aesthetics of the food. The ClO₂ solution can be in the form of a gas, a liquid, or a mist. In further embodiments pertaining to the food industry, this cleaning can also be directed to combating livestock diseases such as hoof and mouth disease and "Mad Cow" disease. In another aspect, the present invention features a method of cleaning food processing equipment that includes the steps of (a) providing a pure ClO₂ aqueous solution, and (b) contacting the food processing equipment with the ClO₂ aqueous solution. It is possible to utilize the aforementioned food industry embodiments by utilizing the solution in a vapor or mist form, as well as administering the solution to the selected surface by washing, wiping, soaking, dipping, soaking, flushing, spraying, immersing, and storing the food products and/or equipment in ClO₂ solution. These methods of administration, while not meant to be limiting, provide a means for disinfecting, sterilizing, sanitizing, aesthetic cleaning, and deodorizing the food industry items. "Food processing equipment" is meant to be defined as all apparatus, food surfaces, carcasses and storage containers pertaining to the harvest of fruits and vegetables, slaughter of meat, poultry fish, their preparation, and distribution to market. This includes, e.g., food processors of all sorts, blenders, mixers, cutting machines and blades, mashers, pulverizers, saws, injectors, curing tanks, cutting boards, cooking utensils, rinsing, draining, or baking apparatuses, and the like.

Horticulture Another preferred embodiment is a method of cleaning horticulture equipment including providing a ClO₂ aqueous solution, and contacting the targeted items with the solution. The horticulture equipment contemplated by this embodiment includes, but is not limited to, irrigation equipment, mister systems, tools, green house equipment, and trays. Additionally, ClO₂ solutions can be added to or generated in fertilizer lines. These solutions are. prefer ably pure solutions because ionic impurities can interact with fertilizers. The solution can be introduced to this equipment by means of washing, soaking, immersing, dipping, bathing, misting, spraying, flushing and storing the horticulture equipment in the ClO₂ solution. As with the previous embodiments, this procedure provides a means for disinfecting, sterilizing, aesthetic cleaning, deodorizing, and ethylene destruction.

In one embodiment, the ClO₂ aqueous solution can also be used for ethylene control or destruction as ClO₂ oxidizes the ethylene double bond. Ethylene gas is a plant hormone that causes it to mature, e.g., vegetable to ripen and flowers to mature. Accordingly, ClO₂ aqueous solutions can be used to retard maturity during shipping and storage of fruits and vegetables. The ClO₂ aqueous solution can be a pure solution, and can be present in a gas over liquid vapor form or a liquid solution that release ClO₂ gas into an atmosphere in which the plants are shipped, e.g., containers, rail cars, trailers and boxes and other shipping containers.

Mold andAlsae

In another embodiment, the present invention provides a method of controlling surface algae and/or mold. The method includes providing a pure ClO₂ aqueous solution and contacting the surface at issue with the solution. The surface can be contacted by means including washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging and storing the mold prone surfaces in the ClO₂ solution. In addition, the mold and/or algae can be contacted by fumigation by ClO₂ gas in a liquid mist or vapor. Thus, surfaces such as greenhouse floors, walls and irrigation lines can be washed with a liquid ClO₂ aqueous solution and then fumigated with a ClO₂ aqueous solution mist. As with the previous embodiments, this procedure provides a means for disinfecting, sterilizing, aesthetic cleaning, and deodorizing the moldy areas.

Cut Flowers One currently preferred embodiment of the present invention is a method of preserving cut flowers. The method includes providing a pure ClO₂ solution and contacting the cut flowers with the solution. This embodiment further provides that a cut flower may be dipped, wiped, washed, soaked, bathed, immersed, sprayed, flushed, sparged, and/or stored in the solution. The cut flowers at issue may be pre- or post- harvest, in a display case, in a transportation carrier, or in a vase. Preferably, the pure solution includes chlorite at a level of less than about 60 ppm, more preferably less than about 50 ppm, even more preferably less than about 40 ppm. Preferably, the pure solution includes chlorate at a level of less than about 50 ppm, more preferably less than 40 ppm, even more preferably less than 30 ppm. In another preferred embodiment, the solution includes chlorite at a level of less than about 30 ppm and more preferably 20 ppm; and/or chlorate at a level of less than about 20 ppm, and more preferably 15 ppm. A pure solution of chlorine dioxide solution has been found to be unexpectedly advantageous over impure solutions. It has been found that the supply of a pure chlorine dioxide solution to prevent microbial growth and blockage of the water-conductive cells in the stem is a key factor in bud opening. Reducing the bacterial count in the vase solution and the plant stems increases the available water and allows the buds to open. In addition the pure chlorine dioxide has proven to be an effective bactericide to prevent microbial growth without causing damage to the plant (phytotoxicity) while increasing the percent of buds that open. In a preferred embodiment, the chorine dioxide in solution is present at a level of from about 2 to 40 ppm in pure solution, more preferably 5 to 20 ppm, even more preferably 5 to 15 ppm. In addition, the presence can be maintained, e.g. , at a level of 2-5 ppm in the solution to extend the life of the flowers. The ClO₂ solution can be in the form of a liquid, a mist, or a gas.

In yet another embodiment of the invention as it pertains to cut flowers, the aforementioned method is directed to ethylene destruction during shipping by providing a ClO₂ solution, as a liquid and/or vapor, and contacting the cut flowers with the solution, e.g., by fumigation. Biofilm

In another embodiment, the present invention provides a method of controlling and/or preventing biofilm growth and accumulation. The method includes the steps of providing a ClO₂ aqueous solution and contacting a biofilm with the solution. Furthermore, this embodiment targets the biofilm by means of washing, wiping, soaking, immersing, dipping, bathing, spraying, flushing, sparging and storing the biofilm prone surfaces in the ClO₂ solution. In a preferred embodiment, the ClO₂ solution is a pure solution, and can be administered in liquid or gaseous form. As with the previous embodiments, this procedure provides a means for disinfecting, sterilizing, aesthetic cleaning, and deodorizing the items contaminated with biofilm. _t In yet another preferred variation, the present invention features a method of controlling biofilm in chillers, consisting of producing a ClO₂ solution and administering the solution to the chillers by means of means of washing, soaking, immersing, dipping, bathing, spraying, flushing and storing the biofilm prone surfaces in the ClO₂ solution.

Water Purification

In yet another embodiment, the present invention features a method of water purification, consisting of providing a ClO₂ solution, and adding the solution to the water. Preferably, the solution is a pure ClO₂ solution. This purification technique may be applied to the purification of water in military uses, camping settings, backcountry hiking, industrial water filtration, personal water filtration, as well as to water storage units. Additionally or alternatively, the ClO₂ solution can be generated in situ in the water storage unit. These water storage units may be tanks containing both potable and non-potable water. The water storage tank can also be a black or gray water tank.

Seawater In another embodiment, the present invention is directed to the cleaning of seawater contact surfaces, e.g., boat hulls. A method of cleaning seawater contact surfaces by providing a ClO₂ solution, administering the seawater contacted surface area with the solution. In a preferred embodiment, the ClO₂ solution is a pure solution. Mold Control

A further embodiment of the present invention is method of mold control in an environment by providing a ClO₂ solution and administering the solution to the environment. Suitable environments include, but are not limited, to hospitals, restaurants, and homes. The solution can be administered by wiping, immersing, bathing, sparging, soaking, washing, dipping, flushing, and spraying surfaces, or by releasing into the air, e.g., by fogging. In a preferred embodiment, the ClO₂ solution pure, and in the form of a ClO₂ gas over vapor or mist.

Surface Disinfecting

In still a further embodiment, the present invention features surface disinfection. This embodiment includes the steps of providing a ClO₂ solution, and administering the solution to the surface area of interest. The surfaces contemplated by the invention include, but are not limited to, hospitals, factories, restaurants, and residential surfaces. Soaking, wiping, immersing, bathing, sparging, washing, dipping, flushing, and spraying any of the areas of interest can be used administer the solution. Preferably, the solution is a pure CiO₂ solution, administered in the foπn of a liquid or gas.

Aviation Another embodiment of the present invention is a novel method of purifying aviation water by providing a pure ClO₂ solution and treating the aviation water with the solution. This is particularly advantageous when refilling with water where potable water is not readily available. In another embodiment, the ClO₂ solution is used to clean aviation storage tanks and/or water lines, whereby the tank or water line is flushed with the ClO₂ solution. The cleaning can be defouling and/or sanitizing.

Recovery of Processed Water

In yet another embodiment, the present invention further features a method of purifying recovered process water by providing a ClO₂ solution and administering the solution to the recovered process water. Preferably, the ClO₂ solution is a pure solution. Dishwashins

Concerning dishwashing (e.g., in restaurants and in the home), the present invention features a method of cleaning dishes that includes providing a ClO₂ solution and administering the solution to the glassware. For example, the glassware could be treated with the ClO₂ solution by bathing, spraying, dipping, wiping, sparging, washing, soaking, immersing, flushing, and/or storing the selected glassware in the ClO₂ solution. In one embodiment the solution is added to a dishwasher, commercial or residential. The solution can further include other cleansing agents. The solution could be in the pure form of the ClO₂ solution in aqueous or a gas solution or any other embodiment listed throughout the application. Preferably, the ClO₂ is in a pure form. Dishwashing is meant to include cleaning plates, eating utensils, glassware, etc. The method is particularly advantageous for glass items when the solution is a pure solution as glass will be cleaned without residue.

Home

In yet another embodiment, the present invention features a method of cleaning in the home. The method includes providing a ClO₂ solution, and cleaning the equipment with ClO₂ solution. The present invention contemplates residential equipment to mean a variety of items including residential surfaces and ducts, and appliances, such as furnaces, humidifiers, air conditioners, telephones, food processors, can openers, and garbage disposal devices. This residential cleaning can occur in areas such as the bathroom and kitchen resulting in deodorizing, sanitizing, disinfecting and sterilization. Washing, wiping, dipping, bathing, sparging, flushing, spraying, soaking, immersing and storing the equipment in the C1O2 solution are contemplated to be within the scope of this embodiment. The ClO₂ solution can be in a pure solution, and can be gaseous or liquid. Preferably, the solution is a pure ClO₂ solution.

Spa

In another embodiment, the present invention features a method of spa equipment cleaning by providing a comprising a ClO₂ solution and contacting the spa equipment with ClO₂ solution. Preferably, the ClO₂ solution is in pure form, and is administered as a liquid or gas. Examples of spa equipment are meant to encompass various items used in the spa setting, such as pools, both swimming and decorative, hot tubs, saunas, pedicure and manicure baths and utensils, and decorative fountains. The method further includes exercise equipment, such as yoga mats, stair-climbers and treadmills. This embodiment deodorizes, sterilizes, sanitizes, disinfects and cleans the equipment. This embodiment can be utilized by washing, dipping, flushing, bathing, immersing spraying, or storing the spa equipment.

Athlete's Foot

In yet another aspect, the present invention features a method for the treatment of a foot fungus by providing a ClO₂ solution and contacting the foot fungus with the solution. In a preferred embodiment, the ClO₂ solution is a pure solution. In another preferred embodiment, the foot fungus is athlete's foot. This painfully itchy condition can be combated by utilizing the present invention by soaking, bathing, washing, spraying, immersing, dipping, wiping, spraying, powdering, flushing or misting the infected area with the solution. Furthermore, this solution can be a pure ClO₂ solution, and can be delivered in the standard forms such as powders, gels, or liquid solution.

Brewery

One embodiment of the present invention features a method of cleaning brewery equipment by providing a ClO₂ solution and exposing the brewery equipment to the ClO₂ solution. Brewery equipment encompasses items which are of use in the production, use, distribution, and consumption of beer. A few examples of brewery equipment are a plate and frame filter, filler line, a diatomaceous earth (DE) filter, a keg, filing heads, beverage cans, beverage bottles, yeast wash equipment, and a growlers (3 gallon beer bottles). The present invention provides means for keg sanitization, growler sanitization, disinfecting, and deodorizing. This innovation can be utilized by dipping, washing, wiping, flushing, spraying, immersing, bathing, soaking, sparging or storing the equipment with the solution. Preferably, the ClO₂ solution is in pure form.

Tavern Yet anbther embodiment of the present invention features a method of cleaning tavern equipment that includes providing a ClO solution and contacting the tavern equipment. In one embodiment, the ClO₂ solution is pure, and can be administered as an aqueous solution, a mist or a gas. Tavern equipment encompasses, but is not limited to glassware, beverage taps, beer taps, beverage lines, and filler lines. Furthermore, a no- rinse sanitizer can represent the present invention. The present embodiment can be utilized by wiping, dipping, washing, immersing, spraying, flushing, soaking, bathing, sparging, or storing the tavern equipment in the ClO₂ solution. This embodiment will provide a tavern with equipment which is deodorized, disinfected, sanitized, sterilized, and clean.

Winery

Another preferred embodiment of the invention features a method of cleaning winery equipment that includes providing a ClO₂ solution and exposing the winery equipment to the ClO₂ solution. Winery equipment encompasses items used in every aspect of wine production, distribution, and consumption. More specifically, the present invention contemplates filter presses, corks, bottles, and glasses. Preferably, the ClO₂ solution is a pure solution, and can be administered as a liquid, a mist, or a gas. The cleaning can be intended to deodorize, sanitize, disinfect and sterilize. The present invention can be applied to the equipment by dipping, washing, soaking, bathing, spraying, immersing, wiping, flushing, sparging or storing in the ClO solution.

Veterinary Clinics Another embodiment of the present invention includes a method of cleaning veterinary clinic equipment that comprises producing a ClO₂ solution, and contacting the veterinary equipment with ClO₂ solution. The equipment can include any surface. The cleaning can include deodorizing, disinfecting, sanitizing, and sterilization. Washing, wiping, bathing, soaking, dipping, flushing, spraying, immersing, sparging and storing the equipment in the C1O2 solution are contemplated to be within the scope of this embodiment. The ClO₂ solution can be in a pure solution, and can be gaseous or liquid. Preferably, the ClO₂ solution is pure.

Military Another embodiment of the present invention includes a method of the destruction of biological agents that includes providing a ClO solution, and contacting a biological agent exposed medium with ClO₂ solution. The medium can include any surface. For example the medium can include air, equipment, apparatuses, or a mammal, such as a human exposed to biological agents. Biological Agents can include, but are not limited to, a fungus, a bacteria such as anthrax, or a virus. Washing, wiping, bathing, soaking, dipping, flushing, spraying, immersing, sparging and storing the affected areas in the C1O2 solution are contemplated to be within the scope of this embodiment. The ClO₂ solution can be in a pure solution, and can be gaseous or liquid. In a preferred embodiment, the solution is a pure ClO₂ solution.

Dental

Another embodiment of the present invention includes a method of treating a dental disorder that includes producing a ClO₂ solution, and contacting an area affected with a dental disorder with the ClO₂ solution. The disorder can include any dental disorder such as plaque, periodontal disease, and/or halitosis. The cleaning can include deodorizing, disinfecting and sterilization. Washing, wiping, soaking, bathing, dipping, flushing, spraying, immersing and sparging the affected area in the C1O2 solution is contemplated to be within the scope of this embodiment. The ClO solution can be in a pure solution, and can be gaseous or liquid. Preferably, the ClO₂ solution is a pure solution.

Treatment of Recycled Water Another embodiment of the present invention includes a method of treating recycled water that includes providing a ClO₂ solution, and contacting recycled water with the ClO solution. The solution preferably is a pure solution. The solution can be administered by direct addition or in a filtration device at any stage in the reclamation process. A device for delivering the ClO₂ solution is also contemplated, such as a device that meters ClO₂ solution over time to clean recycled water as it moves through a stage in the reclamation system.

Shoes

Another embodiment of the present invention includes a method of deodorizing, cleaning and/or decontaminating shoes. The method includes providing a ClO₂ solution, and contacting a shoe with a ClO₂ solution. The ClO₂ solution can be administered by any of the above methods, however, preferably is administered by spraying the ClO₂ solution onto the shoes. Preferably, the solution is a pure ClO₂ solution. The ClO₂ solution can additionally be used for disinfection, sterilization, and sanitization. For example, the solution can be used to clean shoes in a bowling alley.

Sports Equipment Another embodiment of the present invention includes a method of cleaning sports equipment. The method includes providing a ClO₂ solution, and contacting the equipment with the ClO solution. In a preferred embodiment, the ClO₂ solution is a pure solution. The sports equipment can be any sport equipment including, but not limited to, scuba diving equipment, snorkeling equipment, wet suits, and sports helmets, padding, masks, towels and linens. The ClO₂ solution can be administered by any of the above methods, e.g., spraying and immersion. The ClO₂ solution can be used for deodorization, disinfection and sanitization. This method is particularly useful when cleaning neoprene, latex and rubber as conventional cleaning solutions break down these materials. Moreover, conventional solutions can be harmful to the skin, and can fail to kill bacterial and viruses.

Kits

The invention also includes kits for practicing the methods described and claimed herein. The kits include a ClO₂ solution or a precursor to a ClO solution, e.g., a ClO₂ generating device, tablet, or powder, and purified water or other solution.

Preferably the kit includes a pure ClO₂ solution, or a precursor to a pure ClO₂ solution. Preferably, the pure solution includes chlorite at a level of less than about 60 ppm, more preferably less than about 50 ppm, even more preferably less than about 40 ppm; and/or chlorate at a level of less than about 50 ppm, more preferably less than 40 ppm, even more preferably less than 30 ppm. In another preferred embodiment, the solution includes chlorite at a level of less than about 30 ppm and more preferably 20 ppm; and/or chlorate at a level of less than about 20 ppm, and more preferably 15 ppm. The kit can optionally include a means of administering the solution, such as, e.g., a spray bottle, a cartridge, a pump, an atomizer, a vaporizer, an inhaler, or pouch. The dispenser can additionally include a metering device for measuring the amount of ClO administered. The kit optionally can include further cleansing agents such as soap that can be added to the solution. Kits can also include dispensing devices located at the area of cleansing, such as a, laboratory or hospital washing station. EXEMPLIFICA TION

Example 1: Removing Biofilm and Disinfection of Dental Unit Water Lines

A series of tests were conducted on dental unit water lines (DUWLs) often dental chairs that had biofilm buildup in the dental unit water lines, and high microbial levels in the dental unit water. Pure chlorine dioxide solution generated by chlorine dioxide generating devices of the type described in the Hamilton et al. patent application and produced by Selective Micro Technologies LLC (Beverly, MA), were applied at first in three concentrations: 50 parts per million (ppm), 100 ppm and 150 ppm. In later tests, 5 ppm, 25 ppm and 50 ppm solutions were evaluated. The results demonstrated the following:

» Pure chlorine dioxide in water relative to waterline organisms is highly antimicrobial at all concentrations tested.

• Throughout these repeated experiments the DUWLs were challenged between treatments with municipal water and the effluent counts never rose to recoverable levels (>10 CFU), and biofilm matrix never began reestablishment until after the end of the experiments (21 days).

• No emergence of resistant organisms throughout the entire experimental test protocols, and minimum inhibitory concentrations (MICs) and MBCs remained constant as expected.

• 50 ppm chlorine dioxide rendered both the DUWL water samples, and the biofilm itself, sterile within a single overnight treatment.

• In instances of moderate to light established biofilm a single overnight treatment of 50 ppm chlorine dioxide solution was successful in removing approximately 50% of the now sterile matrix.

• Three consecutive overnight treatments successfully eliminated well- established biofilm ranging from 70% to 100%, depending on the density of the established biofilm prior to the initial treatment.

• Chlorine dioxide flushes from the DUWL' s within seconds to less than detectable limits (1 ppm the allowable level; in potable water).

• No taste in the dental unit water or corrosion of the dental equipment was evident. Example 2: Decontamination and Sanitizing Soft Drink Dispensers

At several restaurant locations, there were complaints of off taste, odor and contamination in soft drink dispensers and the soft drinks or water they dispensed. Tests conducted on the fountain units prior to application of the pure chlorine dioxide confirmed the significant presence of microorganisms and algae in the lines.

At each location, the soft drink dispenser lines were filled with 50 ppm pure chlorine dioxide solution generated according to the method described in the Hamilton et al. patent application by product provided by Selective Micro Technologies of Beverly, MA. The lines were filled with the 50 ppm solution until the solution appeared at the discharge (fountain) end of the dispenser. The solution was allowed to stand in the lines for 30 minutes and then rinsed. Tests after the rinse showed all of the algae and nearly all the microorganisms were destroyed. Taste tests after the treatment proved that the deleterious taste effects of the contamination in the lines were eliminated. These tests also confirmed no affect on the taste or presentation of the soft drinks or water dispensed due to the pure chlorine dioxide treatment. Inspection of the equipment showed there was also no corrosion of the equipment due to the treatment.

Example 3: Cleaning and Sanitizing Beer Making Equipment at a Micro Brewery

A series of tests of a 5 ppm pure chlorine dioxide solution generated from product supplied by Selective Micro Technologies (Beverly, MA) to sanitize several sites a micro brewery. All test sites at the brewery had been cleaned and sanitized prior to the tests. Samples were collected at the following locations:

1. City water supply 50μ filtered

2. Growler 3. Jug filler

4. Heat exchange

5. Lager tank

6. Beer line

Several plates were inoculated by swab on site and represent pre- and post- sanitized with chlorine dioxide. All plates were incubated at 37°C. All results are reported in colony forming units per milliliter (CFU/ml). Swabs: Six samples were taken and plated on R2A, EMB and SAB

R2A Plates pre-treatment post-treatment

Growler 146 3 Jug filler 0 2

EMB pre-treatment post-treatment

Growler 0 0 Jug Filler 0 0

SAB pre-treatment post-treatment

Growler 79 0 Jug Filler 0 0

Water Samples: Ten 50 ml samples that were plated on R2A (-1 to -3 dilutions)

R2A Plates pre-treatment post- treatment

Baseline water 50μ filer 0 Growler 20(light, yellow, small) 0 Jug filler 80 (light yellow, small) 0 Heat exchange 550 (40 orange, med; 90 yellow, 0

Small; remainder opaque

Lager tank pre- 0 Beer line 20 (white, large)

All colony types were sub-cultured on R3 A. Identification included Lactobacillus sp. various coccid and several environmental non-pathogenic fungi. The results show the efficacy of the pure chlorine dioxide solution. There was no effect on the taste of the beer.

Example 4: Greenhouse Decontamination Experiments were conducted at two greenhouses. The objectives were to determine: (1) the efficacy of pure chlorine dioxide solution inn disinfecting and decontaminating greenhouse water systems, (2) the efficacy of pure chlorine dioxide solution in removing algae and other contamination from greenhouse floors, (3) the efficacy of using pure chlorine dioxide solution through application through the water system in eliminating pathogens in the greenhouse, and (4) if any of the above uses would harm the plants in the greenhouse. In the first greenhouse the greenhouse water system was filled with 10 ppm pure chlorine dioxide solution and let stand overnight and the solution was then purged from the system. The floors then were power washed with 50 ppm solution. The greenhouse was repopulated for the growing season. The greenhouse water system, the floors and plants were observed for the next 10 weeks. The results are:

• No residuals from the pure chlorine dioxide solution were detected

• No harmful effects on the plants were observed. No phytotoxicity or retarded development.

• There was significant reduction of recurrence of algae on the floors. • The normal plant loss after ten weeks is around 10% loss. In the treated greenhouse, plant loss is less than about 1%. In the second greenhouse, the water system was filled with 10 to 15 ppm solution and allowed to stand overnight and then flushed. The effluent showed that nearly all algae in the system was removed and the system had been sanitized. Observations for five weeks after treatment showed no re-growth of algae. There were no residuals in the system and no deleterious effects on the plants after the greenhouse was repopulated.

In a test to determine if pure chlorine dioxide solution could be used in the "flood floors" where plants are intensely grown. Poinsettias were immersed in 5, 10, 20 and 50 ppm pure chlorine dioxide solutions simulating flood floor conditions. 5, 10 and 20 ppm solutions showed no deleterious effects on the plants.

Example 5: Clinical Analyzer Cleaning and Decontamination

A major clinical analyzer company tested decontamination of fouled clinical analyzers using pure chlorine dioxide solution made from product supplied by Selective Micro Technologies (Beverly MA). Aqueous solutions ranging from 50 ppm to 500 ppm chlorine dioxide were introduced into the analyzers and circulated through it. In all cases, biofilm was removed, microbial counts were significantly reduced and the analyzers performance markedly improved after decontamination. No corrosion was detected and there were no residuals species left in the analyzers. There was no interference with the clinical analyzer operations due to residual chemicals. Example 6: Cleaning and Sanitization of Beer Taps, Lines and Glassware

A test was performed to determine the anti-microbial effectiveness and the effect on taste and presentation of beer using pure chlorine dioxide solution to clean and sanitize beer taps, lines and glassware. 5 ppm and 20 ppm solutions of pure chlorine dioxide solution made from devices produced by Selective Micro Technologies were rinsed through beer lines and taps and to rinse glassware used to serve tap beer. In all cases, the anti-microbial effectiveness of the pure chlorine dioxide solution was at least as good as that of the most common sanitizer (a hypochlorite solution). The pure chlorine dioxide solution did not affect the taste of the beer. The pure chlorine dioxide solution improved the presentation of the beer by significantly extending the duration of the "head" of the tap beer in the glassware.

Example 7: Control of Pathogens and Shelf Life Extension of Propagations Several experiments were conducted to determine the anti-microbial effectiveness, phytotoxicity and other deleterious effects of chlorine dioxide solutions for potted plants and cuttings for propagation. Various varieties of plants and were exposed to 5 ppm, 10 ppm, 20 ppm or 40 ppm aqueous pure chlorine dioxide solution generated from product supplied by Selective Micro Technologies. The following results were observed. • Constant supply of 5 ppm pure chlorine dioxide solution did not retard plant growth and did not produce phytotoxicity.

• Spraying a 40 ppm solution of pure chlorine dioxide on mature petunias and marigolds did not induce phytotoxicity.

• Surface disinfection of cuttings via a quick dip in pure chlorine dioxide solution before placing in the mist house did not injure the cuttings. Rooting was improved when 10 ppm to 20 ppm pure chlorine dioxide solution was used.

• Cuttings had no deleterious effects when placed in 10 ppm pure chlorine dioxide solution. Equivalents

Those skilled in the art will recogmze, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

The entire of all articles, patents and patent application mentioned herein are expressly incorporated herein by reference.

Claims

We claim:

1. A method of cleaning microelectronic components and/or manufacturing equipment, the method comprising the steps of:

(a) providing a ClO₂ solution; and

(b) contacting the microelectronic components and/or manufacturing equipment with ClO₂ solution.

2. The method of claim 1, wherein the ClO₂ solution is an aqueous solution. 3. The method of claim 1, wherein the ClO₂ solution is a gas. 4. The method of claim 1, comprising wiping the equipment with the ClO₂ solution. 5. The method of claim 1, comprising immersing the equipment with the ClO₂ solution.

The method of claim 1, comprising spraying the equipment with the ClO solution.

7. The method of claim 1, comprising storing the equipment with the ClO₂ solution. 8. The method of claim 1, comprising flushing the equipment with the ClO₂ solution.

A method of cleaning a prosthetic, the method comprising the steps of:

(a) providing a ClO₂ solution; and

(b) contacting a prosthetic with the solution.

10 The method of claim 9, wherein the prosthetic is a joint. 11 The method of claim 9, wherein the prosthetic is an endodontic. 12 The method of claim 9, wherein the ClO₂ solution is an aqueous solution. 13 The method of claim 9, wherein the ClO₂ solution is a gas mixture. 14 The method of claim 9, wherein the prosthetic is washed with the ClO₂ solution. 15 The method of claim 9, wherein the prosthetic is soaked in the ClO₂ solution. 16 The method of claim 9, wherein the prosthetic is immersed in the ClO₂ solution. 17 The method of claim 9, wherein the prosthetic is sprayed with the ClO₂ solution. 18 The method of claim 9, wherein the prosthetic is stored in the ClO₂ solution. 19 The method of claim 9, wherein the prosthetic is flushed with the ClO₂ solution. 20 A method of irrigating a wound, the method comprising the steps of:

(a) providing a ClO₂ solution; and

(b) contacting a wound with the ClO₂ solution. 21 The method of claim 20, wherein the wound is a result of an invasive operation.

22. The method of claim 20, wherein the ClO₂ solution is an aqueous solution.

23. The method of claim 20, wherein the ClO₂ solution is a gas mixture.

24. The method of claim 20, comprising soaking the wound in the ClO₂ solution. 25. The method of claim 20, comprising flushing the wound in the ClO₂ solution.

26. The method of claim 20, comprising washing the wound in the ClO solution.

27. The method of claim 20, comprising immersing the wound in the ClO₂ solution.

28. The method of claim 20, comprising spraying the wound in the ClO₂ solution.

29. A method of cleaning the body, the method comprising the steps of: (a) providing a ClO solution; and

(b) contacting the body with the ClO solution.

30. The method of claim 29, wherein the cleaning takes place in a hospital environment.

31. The method of claim 29, wherein the cleaning takes place in a food service environment.

32. The method of claim 29, wherein the cleaning takes place in a dental environment.

33. The method of claim 29, wherein the cleaning takes place in a laboratory environment. 34. The method of claim 29, wherein the ClO₂ solution is an aqueous solution.

35. The method of claim 29, wherein the ClO₂ solution comprises soap, detergent or surfactant.

36. The method of claim 29, wherein the hands are wiped with the ClO₂ solution.

37. The method of claim 29, wherein the hands are immersed with the ClO₂ solution. 38. The method of claim 29, wherein the hands are sprayed with the ClO₂ solution.

39. The method of claim 29, wherein the hands are flushed with the ClO₂ solution.

40. The method of claim 29, wherein the solution is used as a surgical scrub.

41. A method of cleaning aquarium equipment, the method comprising the steps of: (a) providing a ClO₂ solution; and (b) contacting the aquarium equipment with the ClO₂ solution.

42. The method of claim 41 , wherein the equipment comprises a fish tank.

43. The method of claim 41 , wherein the equipment comprises a water regulation system.

44. The method of claim 41 , wherein the equipment comprises an aquatic environment.

45. The method of claim 44, wherein biofilm is removed from the aquatic environment. 46. The method of claim 41 , wherein the ClO₂ solution is an aqueous solution.

47. The method of claim 41 , wherein the ClO₂ solution is a gaseous solution.

48. The method of claim 41 , comprising wiping the equipment with the ClO₂ solution.

49. The method of claim 41, comprising immersing the equipment with the ClO solution.

50. The method of claim 41 , comprising spraying the equipment with the ClO₂ solution.

51. The method of claim 41 , comprising storing the equipment with the ClO₂ solution. 52. The method of claim 41, comprising flushing the equipment with the ClO₂ solution.

53. The method of claim 41, wherein the equipment is sterilized, sanitized, deodorized, or disinfected.

54. A method for preventing or treating a fish disease, the method comprising the steps of:

(a) providing a ClO₂ solution; and

(b) administering the C1O2 solution to an aquatic environment which includes a fish.

55. The method of claim 54, wherein the fish disease is a bacterial infection, a fungus, or a parasite.

56. The method of claim 54, wherein the fish disease is ich, fin rot, saprolegnia, or chilodonella.

57. A method for cleaning equipment, the method comprising the steps of: (a) providing a ClO₂ solution; and (b) contacting the equipment with the ClO₂ solution.

58. The method of claim 57, wherein the ClO solution is a pure solution.

59. The method of claim 57, wherein the ClO₂ solution is an aqueous solution.

60. The method of claim 57, wherein the ClO₂ solution is a gaseous solution.

61. The method of claim 57, wherein the equipment is a medical device or apparatus.

62. The method of claim 61 , wherein the medical device is a pick line, I.N. line, or catheter.

63. The method of claim 61 , wherein the apparatus comprises a scalpel, needle, tweezers, or clamp

64. The method of claim 61 , wherein the medical device comprises a fluid line.

65. The method of claim 64, wherein the fluid line is a blood analyzer line.

66. The method of claim 64, wherein the fluid line is a dialysis machine line.

67. The method of claim 57, wherein the equipment is hospital equipment 68. The method of claim 67, wherein the hospital equipment comprises an endoscope.

69. The method of claim 57, wherein the equipment is clinical equipment.

70. The method of claim 69, wherein the clinical equipment comprises analyzing equipment. 71. The method of claim 69, wherein the clinical equipment comprises gas phase analyzer.

72. The method of claim 57, wherein the cleaning is gas phase decontamination.

73. The method of claim 57, wherein the equipment is glassware.

74. The method of claim 73, wherein the glassware is restaurant, laboratory, or hospital glassware.

75. The method of claim 57, comprising washing the equipment with the ClO solution.

76. The method of claim 57, comprising wiping the equipment with the ClO₂ solution. 77. The method of claim 57, comprising immersing the equipment in the ClO solution.

78. The method of claim 57, comprising spraying the equipment with the ClO solution.

79. The method of claim 57, comprising storing the equipment with the ClO solution.

80. The method of claim 57, comprising flushing the equipment with the ClO solution.

81. The method of claim 57, wherein the equipment is deodorized, sterilized, sanitized, or disinfected.

82. A method of purifying a water system, comprising the steps of: (a) providing a ClO₂ solution; and (b) administering the ClO₂ solution to the water system.

83. The method of claim 82, wherein the water system is a reverse osmosis water system or a deionization system.

84. The method of claim 82, comprising washing the water system with the ClO₂ solution. 85. The method of claim 82, comprising wiping the water system with the ClO₂ solution.

86. The method of claim 82, comprising immersing a component of the water system in the ClO₂ solution.

87. The method of claim 82, comprising spraying the water system with the ClO₂ solution.

88. The method of claim 82, comprising storing the water system with the ClO₂ solution.

89. The method of claim 82, comprising flushing the water system with the ClO₂ solution. 90. The method of claim 82, wherein the water system is deodorized, sterilized, sanitized, or disinfected. 91. A method for treating a lung disease, comprising the steps of:

(a) providing a ClO₂ solution; and

(b) contacting the lungs with the ClO₂ solution. 92. The method of claim 91 , wherein the ClO solution is in the form of a spray, a mist, a vapor or a steam.

93. The method of claim 91 , wherein the ClO₂ solution is administered using a vaporizer, an atomizer or an inhaler.

94. The method of claim 91 , wherein the ClO₂ solution is inhaled. 95. The method of any of the preceding claims, wherein the ClO₂ solution is a pure ClO solution. 96. The method of claim 95, wherein the pure ClO₂ solution comprises less than about 60 ppm chlorite.

97. The method of claim 95, wherein the pure ClO₂ solution comprises less than about 50 ppm chlorate.

98. The method of claim 95, wherein the pure ClO₂ solution comprises less than about 50 ppm chlorite. 99. The method of claim 95, wherein the pure ClO₂ solution comprises less than about 40 ppm chlorate.

100. The method of claim 95, wherein the pure ClO₂ solution comprises less than about 40 ppm chlorite.

101. The method of claim 95, wherein the pure ClO₂ solution comprises less than about 30 ppm chlorate.

102. A kit for practicing a method of any of the preceding claims that includes a ClO solution or a precursor to a ClO₂ solution.

103. The kit of claim 102, wherein the ClO solution is a pure ClO₂ solution.

104. The kit of claim 103, wherein the pure ClO₂ solution comprises less than about 60 ppm chlorite.

105. The kit of claim 103, wherein the pure ClO₂ solution comprises less than about 50 ppm chlorate.

106. The kit of claim 103, wherein the pure ClO solution comprises less than about 50 ppm chlorite. 107. The kit of claim 103, wherein the pure ClO₂ solution comprises less than about 40 ppm chlorate.

108. The kit of claim 103, wherein the pure ClO₂ solution comprises less than about 40 ppm chlorite.

109. The kit of claim 103, wherein the pure ClO solution comprises less than about 30 ppm chlorate.

110. The kit of claim 102 that further includes a device for dispensing the ClO₂ solution.

111. The kit of claim 110, wherein the device is a spray bottle, cartridge, an atomizer, a vaporizer, an inhaler, or a pump. 112. A dispenser for practicing any of the above methods that includes a ClO solution or precursors to a ClO₂ solution. 113. The dispenser of 112, wherein the dispenser contains a metering device.