JP2004532201A - Gas blend of CO2 and Ox and its use for reducing biological burden - Google Patents

Abstract

Disclosed are methods for applying a continuous flow of a gas blend of CO ₂ and O _x and a gas blend of CO ₂ and O _x to a material. The gas blend and the method significantly reduce the biological burden in consumer products (eg, foodstuffs, plant and cosmetic ingredients); in building structures; in shipping containers; and in soil. O ₃ resistant covered transport container tarpaulin (2) (1). The shipping container (1) contains the material (3) to be treated. Transport container (1) via a piping and appropriate control valves, is connected to the O _x generator to (4) at one end, and at the other end is connected to the breaking device (5) I have. The using one fan (6), draw a gaseous _{O x} generator (4) to the transport container (1). Using the second fan (6 '), gas is drawn from the transport container (1) to the destruction device (5). Using a gas analyzer (7), to determine the concentration of O ₃ in the transport container (1).

Description

【Technical field】
[0001]
(Citation of related application)
This application claims priority to still pending U.S. application Ser. No. 09 / 903,685, filed Jul. 13, 2001. U.S. Application No. 09 / 903,685 is a priority over provisional application 60 / 068,668 (filed December 23, 1997) and provisional application 60 / 276,041 (filed March 16, 2001). It is a continuation of the co-pending application Ser. No. 09 / 217,581, filed Dec. 22, 1998, now US Pat. No. 6,284,193.
[Background Art]
[0002]
(Background of the Invention)
(Field of the Invention)
The present invention generally relates to CO2 ₂ And O _x Consumers who have traditionally been treated with gaseous blends with and sterilizers or fumigants commercially available (eg, ethylene oxide, propylene oxide, methyl bromide, hydrogen phosphide, phosphine, steam (heat), radiation, etc.) It relates to a method for applying this gas blend which can be used to significantly reduce the biological burden in products (eg foodstuffs, plant and cosmetic ingredients). CO ₂ And O _x Encapsulation structures, often used for preserving foodstuffs and for reducing biological loads in other commodities and especially soil, using gas blends with and methods for applying this gas blend Biological loading in the body and in shipping containers (eg, wooden pallets and craters) can be reduced.
[0003]
(Technological background)
Damage to food, building structures and other goods by insects and other pests costs millions of dollars annually in the United States. Traditionally, a number of fumigants have been utilized to combat these pests by applying fumigants under a hermetic tarpaulin, in a sealed room, and in a steel chamber. The most widely used fumigants are methyl bromide, hydrogen phosphide and hydrogen cyanide. As disclosed in U.S. Patent Nos. 6,284,193 and 6,334,979, many of these compounds impart hazardous conditions to individuals for application and the food processed. Can form residues that are harmful to goods, building structures, shipping containers and goods. In addition, some of the traditional fumigants have been identified for the formation of carcinogens and mutagens, thereby limiting the products that can be processed. All three primarily used gas fumigants (i.e., methyl bromide, hydrogen phosphide and hydrogen cyanide) all face major regulatory restrictions and / or phasing out. With these limitations in mind, the search for effective alternatives has resulted in the use of materials such as methyl iodide and sulfonyl fluoride. Unfortunately, these alternatives are limited by worker exposure, halogen content and damage to certain commodities.
[0004]
Ozone (O ₃ ) And its main active ingredient (atomic oxygen) have been used for the sterilization of water and commodities for about 100 years. Carbon dioxide (CO ₂ ) Have been used with various insecticides to enhance the effectiveness of the insecticide by increasing the respiration rate of the target organism. However, as discussed in more detail below, O ₃ Or CO ₂ Pre-processing methods using have proven ineffective for many applications.
[0005]
U.S. Patent Nos. 5,624,635 and 5,566,627 disclose O.D. ₃ Disclosed are methods and apparatus for the use of.
[0006]
U.S. Patent Nos. 4,889,708; 5,403,597; 5,897,841 and 6,027,667 disclose CO2 as a carrier gas for phosphine fumigants. ₂ Disclose the use of
[0007]
U.S. Pat. No. 4,200,656 discloses CO2 as a carrier for methyl bromide in fumigation. ₂ Disclose the use of
[0008]
U.S. Pat. No. 4,998,377 discloses CO2 as a carrier for methyl bromide and hydrogen phosphide in fumigation. ₂ Disclose the use of
[0009]
U.S. Patent No. 5,678,352 discloses CO2 as a carrier for toxic agents such as methyl bromide during fumigation. ₂ Disclose the use of
[0010]
U.S. Pat. No. 5,464,457 discloses ammonia and CO2 for fumigation of a section of soil. ₂ Disclosed is the use of an ammonium carbonate component that decomposes.
[0011]
U.S. Pat. No. 4,989,363 discloses pesticidal amounts of CO for fumigation. ₂ Disclose the application of The process disclosed in U.S. Pat. No. 4,989,363 provides a process for reducing CO2 over a period of at least about 5 days. ₂ Need to be administered.
[0012]
U.S. Pat. No. 5,011,699 discloses O.sub.O at a specified ratio (i.e., 1: 2 to 2: 1) for sterilizing foodstuffs at low temperatures. ₃ And CO ₂ Disclose the use of
[0013]
U.S. Patent No. 6,066,348 discloses O.sub.O at low temperatures for disinfecting foodstuffs. ₃ And CO ₂ Disclose the use of
[0014]
Japanese Patent Publication No. 0207562A (abstract) discloses an O.S. ₃ , CO ₂ And the use of N gas is disclosed.
[0015]
U.S. Patent Nos. 6,283,193 and 6,334,979 teach an oxygen-containing gas (i.e., O2) in a vacuum chamber to reduce the biological burden on foodstuffs and other goods. ₃ , O ₂ And O ₁ (Hereinafter, O _x )) Are disclosed. O _x Although such use of has proven successful in controlling insect and microbiological concerns about selected fruits, vegetables and other plants, the problem of phytotoxicity and O ₃ The need to treat food and other commodities that cannot withstand processing under reduced pressure remains due to the fact that they are easily converted to oxygen when exposed to an oxygen-rich atmosphere. I have.
DISCLOSURE OF THE INVENTION
[Means for Solving the Problems]
[0016]
The present inventors have determined that for a number of commodities, whether a vacuum is used or not, the specified ratio (ie, about 90% to about 99% CO 2 ₂ And about 1% to about 10% O _x , Preferably from about 98% to about 99% CO ₂ And about 1% to about 2% O _x CO) ₂ And O _x It has been surprisingly found that gas blends with are very effective at reducing biological loads. This surprising finding indicates that gaseous O _x Is applicable.
[0017]
(Summary of the Invention)
It is desirable to process a wide variety of materials in a cost effective manner. CO ₂ And O _x And the method for applying the gas blends of the present invention involve fumigation of the product at the location where the product is typically stored (hereinafter referred to as "biological load reduction"). Enable, thereby eliminating the need to move the goods to another location for processing.
[0018]
The method of the present invention provides a CO 2 ₂ And / or O ₃ CO2 in a technically advanced system that overcomes previously encountered limitations in processing ₂ And O _x Use a gas blend with Most importantly, the method of the present invention eliminates the need for complex systems often used in prior art methods. This method can be used in the field, thereby obviating the need to move the material to a special processing location.
[0019]
Therefore, the object of the present invention is ₂ And O _x Gas blend with CO and CO ₂ And O _x To provide a method for reducing the biological load from food and other goods, building structures, shipping containers and soil by applying a gas blend with the same.
[0020]
Another object of the present invention is to provide CO 2 ₂ And O _x Gas blend with CO and CO ₂ And O _x To provide a method for reducing the biological load from food and other goods, building structures, shipping containers and soil in a safe manner by applying a gas blend with the same.
[0021]
It is therefore an object of the present invention to eliminate the health risks associated with reducing the biological load from foodstuffs and other goods, building structures, shipping containers and soil.
[0022]
A further object of the present invention is to provide a simple, efficient and economical CO 2 ₂ And O _x Blends with CO, to reduce the biological load from food and other goods, building structures, shipping containers and soil that can be used on site ₂ And O _x And to provide a method for applying a gas blend with the same.
[0023]
In accordance with these and other objectives, the gas blends of the present invention comprise from about 90% to about 99%, preferably from about 98% to about 99% CO2. ₂ And about 1% to about 10%, preferably about 1% to about 2% O _x Consists of The method of the present invention for applying a gas blend involves the use of CO 2 ₂ Gas and O _x Applying a continuous stream of gas to the material. Preferably, the gas blend is applied at an elevated temperature (e.g., from about 45F to about 140F, and more preferably from about 85F to 115F).
[0024]
CO ₂ Gas and O _x A continuous stream of gas can be prepared by any means. For example, O _x The continuous flow of gas is about 20 lbs / in ² O at pressure less than _x O including means for generating a gas (eg, one or more of the following) _x It can be prepared in a production cell: corona discharge, discharge, ultraviolet light, X-rays, radioisotopes and electron beams. CO ₂ And lower concentrations of CO _x O before generation _x Can be added to the production cell or ₂ Immediately after its formation _x It can be mixed into a gas stream.
[0025]
CO ₂ And O _x After application of the gas blend to the material, the gas blend is then passed through a commercial catalytic breaker to release any remaining CO, O, before releasing the gas stream to atmosphere. ₃ And O ₁ Can be removed.
[0026]
The invention also relates to the CO2 of the invention. ₂ And O _x Food products and other commodities, building structures, shipping containers and / or soil obtained from the use of gas blends and methods with the same.
[0027]
Additional objects and attendant advantages of the invention will be set forth in this description and the examples below, or may be learned from using gas blends or practicing the methods of the invention. These and other objects and advantages may be realized and obtained by the features, means, and / or combinations specifically described herein. It is also to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not to be construed as limiting or limiting the invention.
[0028]
The invention itself, together with further objects and attendant advantages, will be best understood by reference to the following detailed description when taken in conjunction with the accompanying drawings.
[0029]
In the description that follows, like parts are designated by like reference numerals throughout the drawings.
[0030]
(Description of a preferred embodiment)
All patents, patent applications, and documents that may be cited herein are hereby incorporated by reference.
[0031]
O ₃ Has been recognized for many years. O ₃ Is widely used as a disinfectant for sewage treatment and for purification of drinking water. However, it was not adopted as a biological load reduction treatment. The main cause of this rejection is O ₃ If the molecule is very unstable and does not encounter a reactive sensitive substrate, ₂ Is to be converted quickly. O ₃ It also has the ability to react with a wide range of substrates and is expected to react with the packaging material around the article to be treated. This further results in O reacting with the microbial contaminants to inactivate the microbial contaminants. ₃ Decrease the number of molecules.
[0032]
U.S. Patent Nos. 5,011,699 and 6,066,348 disclose O.M. ₃ And the material to be treated is ₃ Including relying on exposure for various periods of time in a static manner without supplementing ₃ Discloses an earlier attempt to use as a biological load reduction treatment. Under these conditions, the O ₃ The concentration of O ₃ Due to the short half-life of, which is typically less than 20 minutes, it is expected to drop quickly to lower levels than required for effective biological load reduction. A further disadvantage of the static exposure technique is that O 2 fills voids and interstices of the material being processed through the packaging material. ₃ It is to rely on simple diffusion to facilitate the penetration of molecules. Therefore, such a method requires O 2 ₃ Does not achieve proper permeation of molecules.
[0033]
The method of the present invention provides for CO 2 throughout the processing cycle. ₂ Continuous flow and O _x Through the packaging material and through the packaging material into the voids and interstices of the material to be treated. _x Provides a significant advance over the prior art static biological load reduction techniques in that it facilitates the rapid permeation of thiol. CO ₂ Flow is between about 90% and about 99%, preferably between about 98% and about 99%; _x Is between about 1% and about 10%, preferably between about 1% and about 2%. Newly generated O _x Continuous supply of molecules to provide inert O ₂ By substituting molecules that have naturally degraded into and molecules that have reacted during this process, _x Ensure that the concentration remains essentially the same throughout the process.
[0034]
The method of the present invention also offers significant cost advantages over existing biological burden reduction techniques. The most notable savings are CO ₂ And O _x Derived from the fact that gas blends with can be generated and applied in situ.
[0035]
O _x The facility is neither flammable nor explosive, so the facility does not require damage-limiting structures or explosion-proof equipment. Another advantage of the method of the present invention is that cleaning is easily accomplished using existing techniques. Furthermore, O ₃ Has been classified by the US Food and Drug Administration as generally recognized as "GRAS".
[0036]
CO of the present invention ₂ And O _x Gas blends and methods with have proven successful in processing a wide variety of materials, including food and other commodities, building structures, shipping containers and soil.
[0037]
The method of the present invention avoids many of the limitations of previous implementations by avoiding the need for watering and / or flooding the material to be treated. Many products such as spices, powder-based products, sugar-based products, cosmetic bases, herbs and plants, all of which are sensitive to high levels of moisture, are processed using the methods of the present invention. obtain. The method of the present invention also avoids the need to open conventional commercial packaging before processing, thereby avoiding unnecessary product degradation and loss. The product can be processed in situ utilizing conventional processing. Previous methods required that the product be agitated, blended, whipped or repackaged during or shortly after completion of the process. O _x The extended half-life of the radicals allows the active portion of the process gas to penetrate well into the material and act on the offending organism. CO ₂ In combination with the stabilized O _x The gas mixture is impregnated with O _x Even in the presence of gas, it is further enhanced by the increased respiration rate of the pest.
[0038]
According to one embodiment, the gas mixture comprises mainly CO 2 ₂ And lower concentrations of O ₃ , O ₂ And carbon monoxide (CO). This gas mixture is preferably supplied to an ozone generator (eg, CO 2 ₂ , O ₃ , O ₂ And a gas blend consisting of CO and CO is formed. The gas blend decomposes this triatomic form of oxygen back to its diatomic form (atmospheric oxygen). ₃ By reducing molecular collisions of molecules, O ₃ Helps stabilize the molecule. Several advantages have been observed by producing this gas blend. The first advantage is that O ₃ Of the material to be treated, thereby having the opportunity to penetrate into the internal gap of the material being processed. In addition, CO ₂ Acts as a non-polar solvent to help the gas blend penetrate into the material. By reducing residual oxygen levels below normal atmospheric levels, oxidative damage to the material is greatly reduced. High levels of CO ₂ Presence enhances the effects of fumigants by promoting insect respiration, thereby allowing fumigants to be injected into the insect respiratory tract and coming into direct contact with insect body fluids It is shown.
[0039]
Alternatively, CO ₂ Immediately after the ozone generator ₃ It can be mixed into the enriched gas stream to assist in forming a gas blend. According to this technique, no CO is formed. Because CO ₂ This is because none of the molecules are cleaved. The disadvantage of this system is that O ₃ Required to produce the oxygen (which is then ₃ Is allowed to decompose at an accelerated rate).
[0040]
This gas blend allows it to flow as a continuous stream into, through, and out of an impervious tarpaulin or enclosure over a period of time. Utilizing a fan, the gas blend may be dispersed throughout the enclosed area to provide permeation to the treated goods. The outlet for excess gas is ₃ , O ₁ And a constant release of gas through a catalyst bed consisting of, for example, manganese oxide, copper oxide and aluminum oxide, which destroys CO. This process has been demonstrated to operate at temperatures between 45 ° F and 140 ° F. A heating device may be incorporated into the fan to help bring the temperature of the material to a desired temperature. Ideal temperatures are between 85F and 115F.
[0041]
Products and the like generally require 1 hour to 24 hours of processing if other products (e.g., grains) may require more than 48 hours of processing. O _x The concentration as measured directly from the generator is about 90% to 100% CO ₂ By using a starting gas mixture of oxygen or air, preferably about 98% to 99%, and about 0% to 10%, preferably about 1% to 2%, for foodstuffs. , More preferably within the range of about 10 ppm and 1,800 ppm, and up to about 20,000 ppm for building structures, shipping containers and soil. The gas stream flowing through the ozone generator must be very dry, but no additional moisture is needed to humidify the material to be treated.
[0042]
Agricultural soil can be treated according to the method of the present invention, wherein CO 2 ₂ And O _x Gas blends with gas impermeable membranes (eg, O 2 ₃ It is supplied continuously under a polyethylene film or fumigation waterproof fabric which has proven to be resistant. This process is typical of methyl bromide soil fumigation conventionally performed to control various insects, weed seeds, nematodes and fungal infections. After application, CO ₂ And O _x The gas blend with is destroyed at the outlet port.
[0043]
Parasitized structures can also be treated according to the method of the present invention, where the structures are first covered with a gas impermeable membrane and the leak is sealed, and then the CO 2 ₂ And O _x Is continuously supplied and dispersed into the structure. The gas blend is homogeneously dispersed using a fan, which can also be used to supply any necessary additional heat. After application, CO ₂ And O _x The gas blend with exits the exhaust and is destroyed using a destruction device.
[0044]
Referring to FIGS. 1 and 2, the present invention provides, for example, ₃ An apparatus that can be used to carry out this method if it comprises a shipping container 1 (FIG. 1) or a storage container 1 ′ (FIG. 2) covered with a resistant waterproof cloth 2. The transport container 1 (or storage container 1 ') contains the material 3 to be processed. The transport container 1 (or storage container 1 ') is connected at one end via pipes and appropriate control valves. _x It is connected to a generator 4 and to the destruction device 5 at the other end. Using the first fan 6, the gas is _x Withdraw from the generator 4 to the transport container 1 or the storage container 1 '. With the aid of the second fan 6 ′, gas is withdrawn from the transport container 1 or the storage container 1 ′ to the breaking device 5. Either the first fan 6 or the second fan 6 'may include a heating means (not shown) for bringing the transport container 1 or the storage container 1' to a desired temperature. Using the gas analyzer 7, the O in the transport container 1 or the storage container 1 ' ₃ Is determined.
[0045]
Referring to FIGS. 1 and 2, according to one embodiment of the invention, the material 3 to be reduced in biological load is placed in a transport container 1 or a storage container 1 '. The desired temperature is maintained via heating means (not shown). The process then proceeds to O _x It is started by activating the generator 4. CO ₂ Gas flow (this is O _x Can be added to the generator 4 or can be added after generation) and then CO 2 ₂ Gas and O _x Gas is drawn into, through and out of the transport container 1 or the storage container 1 'via the first fan 6 and the second fan 6'. O _x The generator 4 operates continuously during this process.
[0046]
CO ₂ And O _x Exposure to a gas mixture can vary from minutes to hours, depending on the material to be treated. Once the biological load reduction phase is completed, O _x The generator 4 is deactivated and fresh air is forced into the transport container 1 or the storage container 1 '. All of the gas may then pass through the destruction device 5, which may release any residual CO, O before the gas stream is discharged to the atmosphere. ₃ And O ₁ Is removed. The treated material 3 is then ready for use after a suitable test confirming a reduced biological load.
[0047]
According to the present invention, the material is O 2 under atmospheric conditions. _x And CO ₂ By applying a continuous stream of This allows, for example, processing of the material beneath the tarp or in a sealed chamber, thereby eliminating the need for a vacuum chamber.
【Example】
[0048]
The present invention is further illustrated by the following non-limiting examples.
[0049]
(Example 1)
CO of the present invention ₂ And O _x Alfalfa pellets for animal samples were processed using a gas blend and method with a. The alfalfa pellets were heavily infected with saw-toothed grain beetles (adults, maggots and eggs). The alfalfa pellets were placed in a breathable paper bag (sewing) and placed in a processing room equipped with two circulating fans and a heating system. The gas blends described below were flowed through this chamber. The following parameters were used:
Gas mixture: 99.5% CO ₂ And 0.5% O ₂ (O ₃ Mixed before generation)
Room temperature: 95 ° F
Relative humidity: maintained below 20%
Last O ₃ Concentration: 650 ppm
Total gas exposure time: 16 hours
O ₃ Generation technology: Corona discharge
(result)
Alfalfa pellets were observed for 60 days after treatment. No second intrusion into this product and no damage was observed.
[0050]
(Example)
CO of the present invention ₂ And O _x Papaya fruit artificially loaded with Drosophila Drosophila (adults only) was processed using a gas blend and method with The fruit was placed in a regular shipping crate constructed from cardboard. Drosophila were placed in small glass tubes filled with tissue and placed at various locations in the shipping crate. The following parameters were used:
Gas mixture: 98% CO ₂ And 2% O ₂ (O ₃ Mixed before generation)
Chamber temperature: 85 ° F
Relative humidity: maintained below 20%
Last O ₃ Concentration: 1,100 ppm
Gas exposure time: 60 minutes
O ₃ Generation technology: Corona discharge
(result)
All flies were killed in this process. No damage to the fruit was observed.
[0051]
(Example)
CO of the present invention ₂ And O _x Fresh strawberries were processed using a gas blend and method with. This strawberry was used for 100,000 E. coli. E. coli was immersed in a buffered aqueous solution containing the starting titer. The strawberries were allowed to air dry and placed in a processing chamber with several tubes containing live aphids. The insects were kept in a glass tube filled with tissue. Control set plated strawberries were kept at room temperature for later counting. The following parameters were used:
Gas mixture: 98% CO ₂ And 2% O ₂ (O ₃ Mixed before generation)
Chamber temperature: 112 ° F
Relative humidity: maintained below 20%
Last O ₃ Concentration: 1,600 ppm
Gas exposure time: 60 minutes
O ₃ Generation technology: Corona discharge
(result)
All insects were killed during this process. Strawberries in the control set are 6,846 cfu / inch ² At a concentration of E. tested positive for E. coli. The treated strawberries tested negative and had no damage to the fruit and carpel.
[0052]
CO of the present invention ₂ And O _x Blend with CO and CO ₂ And O _x The method for applying gas blends with is a good alternative to commercial sterilants and fumigants in all of the current uses of commercial sterilants and fumigants. The gas blends and methods of the present invention are also useful for the treatment of many food ingredients that do not permit the use of commercially available sterilants and fumigants, including cocoa beans, grains and edible gums. CO of the present invention ₂ And O _x Examples of commodities to be processed using the gas blends and methods with are:
Fresh fruits and vegetables, and dried fruits and vegetables,
Herbs and plants,
Dried pet food,
Cotton and other fibers,
Wood and wooden products,
grain,
Livestock feed,
Transportation,
Nursery rootstock, and
Ornaments and cut flowers.
[0053]
Although the present invention has been described in some detail with respect to preferred embodiments thereof, many modifications can be made and many alternative embodiments can be derived without departing from the scope of the invention.
[Brief description of the drawings]
[0054]
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates CO 2 in accordance with the method of the invention. ₂ And O _x FIG. 4 is a schematic diagram illustrating an embodiment of a method for reducing biological burden using a continuous flow of.
FIG. 2 shows a graph of CO 2 in accordance with the method of the present invention. ₂ And O _x FIG. 4 is a schematic diagram illustrating another embodiment of a method for reducing biological load using a continuous flow of.

Claims (14)

A method for fumigating an encapsulated structure to reduce the biological burden in the structure, comprising:
The gas blend of O _x and CO _2, comprising the steps of releasing the the encapsulated structure, the gas blend, from about 1% to about 10% of _{O x} and from about 90% to about 99% of the CO ₂ including,; and the said gas blend of O _x and CO ₂ in the encapsulated structure in comprising the step of maintaining a time sufficient to lower the biological loading of the structure and method . The gas blend comprises about 1% to about 2% _{O x} and about 98% to about 99% CO _2, The method of claim 1. A method for fumigation of a material contained in an enclosed space to reduce a biological load, comprising:
The gas blend of O _x and CO _2, comprising the steps of releasing the said sealing space, the gas blend, from about 1% to about 10% of _{O x} and from about 90% to about 99% of the CO ₂ including,; and the said gas blend of O _x and CO _2, into the sealed space, comprising the step of maintaining a time sufficient to reduce the biological burden in material, process. The gas blend comprises about 1% to about 2% _{O x} and about 98% to about 99% CO _2, The method of claim 3. A method for fumigation of soil in a field to reduce biological load, comprising:
Placing a gas impermeable membrane on the soil to provide a sealed space on the soil;
The gas blend of O _x and CO ₂ comprising the steps of releasing the said sealing space, the gas blend comprises from about 1% to about 10% of _{O x} and from about 90% to about 99% of CO _2, process involving, and the gas blend of O _x and CO _2, in said sealing space, a step of maintaining for a sufficient time to reduce the biological loading of the soil, method. The gas blend comprises about 1% to about 2% _{O x} and about 98% to about 99% CO _2, The method of claim 5. A fumigant system including a gas blend of O _x and CO _2, the gas blend comprises from about 1% to about 10% of _{O x} and from about 90% to about 99% of CO _2, system. The gas blend comprises about 1% to about 2% _{O x} and about 98% to about 99% of CO _2, according to claim 7 system. A method for fumigating a material, comprising:
Placing the material in a sealed space; and applying a continuous stream of O _x and CO ₂ through the sealed space, wherein the O _x comprises oxygen and its radicals, and x is , Which is an integer from 1 to 3. 10. The method of claim 9, wherein the temperature in the enclosed space is maintained between about 45F and about 140F. 11. The method of claim 10, wherein the temperature in the enclosed space is maintained between about 85F to about 115F. It said O _x is generated in the O _x generation cell, wherein the CO ₂ is introduced into the O _x generation cell before the O _x generation method according to claim 9. It said O _x is generated in the O _x generation cell, wherein the CO ₂ is introduced after the generation of said O _x, A method according to claim 9. The CO ₂ and the _{O x} is the _{O x} drawn from generating cell to the sealed space; wherein the CO ₂ and the _{O x} is drawn from said sealing space A method according to claim 12.

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