NZ796006A - Decontamination device and method using ultrasonic cavitation - Google Patents

Decontamination device and method using ultrasonic cavitation

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Publication number
NZ796006A
NZ796006A NZ796006A NZ79600617A NZ796006A NZ 796006 A NZ796006 A NZ 796006A NZ 796006 A NZ796006 A NZ 796006A NZ 79600617 A NZ79600617 A NZ 79600617A NZ 796006 A NZ796006 A NZ 796006A
Authority
NZ
New Zealand
Prior art keywords
mist
cleaning fluid
decontamination
reservoir
plasma
Prior art date
Application number
NZ796006A
Inventor
Halden Stuart Shane
Johnny Sullivan Cato
Charles Liu
Original Assignee
Tomi Environmental
Filing date
Publication date
Application filed by Tomi Environmental filed Critical Tomi Environmental
Publication of NZ796006A publication Critical patent/NZ796006A/en

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Abstract

method and apparatus for decontaminating substantially enclosed environments by using ultrasonic cavitation of a cleaning fluid to produce a low pressure, low air flow mist that can be activated by a nonthermal plasma actuator to create a cloud of activated hydroxyl species with the capacity to decontaminate articles, open surfaces or substantially enclosed spaces of pathogens, including bacteria, and other pathogenic microorganisms. An automated system and related non-transitory computer medium are also disclosed.

Description

A method and tus for decontaminating substantially enclosed environments by using ultrasonic cavitation of a ng fluid to produce a low re, low air flow mist that can be activated by a nonthermal plasma actuator to create a cloud of activated hydroxyl species with the capacity to decontaminate articles, open surfaces or substantially enclosed spaces of pathogens, including bacteria, and other pathogenic microorganisms. An automated system and related nontransitory computer medium are also disclosed.
NZ 796006 TITLE DECONTAMINATION DEVICE AND METHOD USING ULTRASONIC CAVITATION FIELD The present application relates generally to an apparatus and method for decontaminating articles, enclosed spaces, and unenclosed spaces and, more ularly, to microbiological amination of such locations.
BACKGROUND Microbiological species are widely distributed in our nment. Most microbiological species are of little concern, because they do not damage other living organisms.
However, other microbiological species may infect man or animals and cause them harm. The removing or rendering ineffective of ous microbiological organisms has long been of interest. Drugs and medical devices are ized and packaged in sterile containers. Medical environments such as operating rooms, wards, and examination rooms are decontaminated by various cleaning procedures so that injurious microbiological organisms cannot spread from one patient to another.
Many available technologies for lling microbiological organisms are of limited value in the public health circumstances of biological warfare and rorism.
Furthermore, current technologies addressing these instances are limited in their effectiveness in tightly ed environments. A new approach is needed that is more readily usable in tightly enclosed nments, as well as retaining the ability for use on open surfaces in large spaces, with enhanced kill, and simpler maintenance of machinery. The present invention fulfllls this need, and r provides related advantages.
An aspect of the application is directed to a method for decontaminating an article, surface, or substantially enclosed space, comprising the steps of: shearing a cleaning fluid into a mist comprising aerosol droplets accumulating in a top chamber portion of a substantially closed chamber comprising a funnel shaped top chamber portion, a bottom chamber portion, a side chamber portion and an interior chamber portion, n the cleaning fluid is sheared by ultrasonic cavitation, subjecting the mist to a nonthermal plasma actuator to form plasma activated ionic particles, and contacting the article, surface, or substantially enclosed space to the plasma ted ionic particles.
One other aspect of the application is directed to a method for decontaminating an article or substantially enclosed space, comprising the steps of: ng a ng fluid into a mist comprising l droplets by cavitating the cleaning fluid using an ultrasonic cavitator submerged in a substantially closed chamber comprising the cleaning fluid; subjecting the mist to a nonthermal plasma actuator in an outlet tube extending from an opening in a top chamber portion of the substantially closed chamber, wherein the outlet tube comprises a hollow lumen with a distal opening above the top chamber portion for expelling the aerosol droplets to form plasma activated ionic particles; and contacting the article or substantially enclosed space to the plasma activated ionic particles.
Another aspect of the application is directed to a amination tus comprising: a substantially closed chamber comprising a funnel shaped top chamber portion, a bottom chamber portion, a side chamber n and an or chamber portion, an ultrasonic cavitator comprising a proximal end and a distal end, the al end being connected to the bottom chamber n, the distal end extending into chamber interior, the cavitator comprising a piezoelectric transducer to vibrate a material at a resonant frequency, thereby generating a plurality of sheared fluid les, an inlet tube feeding into the side chamber portion, the tube configured so that a ng fluid can passively lie in the bottom chamber portion and submerge the distal end of the ultrasonic cavitator so that the sheared fluid particles flow upward through the cleaning fluid and across the liquid-air interface, forming a mist of aerosol droplets accumulating in the top chamber portion, an outlet tube extending from an opening in the top r portion, the outlet tube sing a hollow lumen with a distal opening above the top chamber n for expelling the aerosol droplets, and a rmal plasma actuator comprising one or more electrodes adjacent to the distal opening, the electrodes configured to generate a high voltage pulse activating the aerosol droplets to form plasma activated ionic particles for decontaminating an article, surface, or substantially closed space.
A further aspect of the application is a method for decontaminating an article or substantially enclosed space, comprising the steps of: submerging an ultrasonic cavitator in a reservoir of a cleaning fluid, cavitating the cleaning fluid with ultrasonic vibrations produced by the ultrasonic cavitator, generating a mist comprising aerosol droplets, wherein the mist is generated from the cleaning fluid while the cleaning fluid is being ted, subjecting the mist to a nonthermal plasma actuator to form plasma activated ionic particles, and contacting the plasma activated ionic particles to a pathogen.
One other aspect of the application is a method for decontaminating an e or substantially enclosed space, comprising the steps of: providing a oir of a cleaning fluid, cavitating the reservoir of cleaning fluid by ng force to the cleaning fluid, generating a mist comprising aerosol droplets, wherein the mist is generated from the cleaning fluid while the cleaning fluid is subject to cavitation by force, subjecting the mist to a nonthermal plasma or to form plasma activated ionic particles, and contacting the plasma activated ionic WO 32991 particles to a pathogen.
An additional aspect of the application is an apparatus for decontaminating an article or substantially enclosed space, comprising: a reservoir of cleaning fluid; an ultrasonic cavitator; wherein the ultrasonic cavitator is submerged in the reservoir; a nonthermal plasma or, wherein the actuator activates a mist generated from the reservoir; a pathway that connects the nonthermal plasma activator to the reservoir; an outer tube; wherein the outer tube ts the nonthermal actuator to the external atmosphere; and wherein a mist generated from the reservoir can pass through the funnel to the actuator; and further wherein after the mist is activated by the actuator the mist can pass through the outer tube to the al atmosphere.
A further aspect of the application is a method for decontaminating a substantially enclosed space; comprising the steps of: sensing a ce of an airborne pathogen in the atmosphere of a substantially enclosed space using a sensor; communicating the presence of the airborne pathogen from the sensor to a networked computer sor; communicating from the networked er processor to a decontamination apparatus that an airborne pathogen is present in the substantially enclosed space; activating a decontamination cycle of the decontamination apparatus; wherein the decontamination cycle comprises the steps of: providing a reservoir of a cleaning fluid; cavitating the reservoir of cleaning fluid by applying force to the cleaning fluid; generating a mist comprising aerosol droplets; wherein the mist is generated from the cleaning fluid while the cleaning fluid is t to cavitation by force; subjecting the mist to a nonthermal plasma actuator to form plasma activated ionic particles; and contacting the plasma activated ionic particles to the ne pathogen.
An onal aspect of the application is a system for decontaminating a substantially enclosed space; comprising: a sensor for airborne pathogens; n the sensor is in networked communication with a er processor; a computer processor; wherein the computer processor is in ked communication with the sensor and a decontamination apparatus; a decontamination apparatus; wherein the decontamination apparatus is in networked communication with the er processor; and further wherein the decontamination tus comprises: a reservoir of cleaning fluid; an ultrasonic cavitator; wherein the ultrasonic cavitator is submerged in the reservoir; a nonthermal plasma actuator; wherein the actuator activates a mist generated from the reservoir; a pathway that connects the nonthermal plasma activator to the reservoir; an outer tube; wherein the outer tube connects the nonthermal actuator to the external atmosphere; and wherein a mist generated from the reservoir can pass through the funnel to the actuator; and further wherein after the mist is activated by the actuator the mist can pass h the outer tube to the al atmosphere.
A still r aspect of the application is a non-transitory computer readable medium providing instructions for repeating decontamination cycles of a decontamination apparatus, the instructions comprising: sensing a presence of a pathogen in a substantially enclosed space; communicating the presence of the pathogen to a computer database; identifying the pathogen sensed in the substantially enclosed space using the computer database; selecting a program of decontamination cycles from the computer database based on the ty of the pathogen; communication the selected program to a decontamination tus; wherein the decontamination apparatus is networked to automatically follow the program; performing the decontamination cycles according to the program; wherein each decontamination cycle comprises the steps of: providing a reservoir of a cleaning fluid; cavitating the reservoir of cleaning fluid by applying force to the cleaning fluid; generating a mist comprising aerosol droplets; wherein the mist is ted from the cleaning fluid while the cleaning fluid is subject to cavitation by force; subjecting the mist to a nonthermal plasma or to form plasma activated ionic particles; and contacting the plasma activated ionic particles to the airborne A further aspect of the application is a method comprising the step of exposing the substantially enclosed space to a ant gas comprising chlorine dioxide; ethylene oxide; ozone; propylene oxide; nitrogen dioxide; formaldehyde or a combination f. In some embodiments; the cleaning fluid comprises hydrogen peroxide at a concentration between 6 to 9%. In particular embodiments; the cleaning fluid comprises hydrogen peroxide at a concentration of about 7.8%. In some embodiments; the article or substantially closed space is exposed to the plasma activated ionic particles in an amount ent to provide greater than 6- log10 ion of viable bacteria or viable bacterial spores relative to untreated controls. In particular ments; the article; surface; or substantially closed space is exposed to the plasma activated ionic particles in an amount sufficient to provide greater than 0 killing of bacteria or bacterial spores relative to untreated controls. In other embodiments; the article; surface; or substantially closed space is exposed to the plasma activated ionic particles in an amount sufficient to e greater than 8-log10 killing of bacteria or bacterial spores relative to ted controls. In another embodiment; the e; surface; or substantially closed space is exposed to the plasma activated ionic particles in an amount sufficient to provide greater than 9- log10 killing of bacteria or bacterial spores ve to ted controls.
Another aspect of the ation is a decontamination apparatus comprising: a substantially closed chamber comprising a funnel shaped top chamber portion; a bottom chamber portion; a side chamber portion and an or chamber portion; an ultrasonic cavitator comprising a proximal end and a distal end; the proximal end being connected to the bottom chamber portion; the distal end extending into r interior; the cavitator comprising a piezoelectric transducer to vibrate a material at a resonant frequency, thereby generating a plurality of sheared fluid particles; an inlet tube feeding into the side chamber n, the tube configured so that a cleaning fluid can passively lie in the bottom chamber n and submerge the distal end of the ultrasonic cavitator so that the sheared fluid particles flow upward through the cleaning fluid and across the liquid-air interface, g a mist of aerosol droplets accumulating in the top r portion, an outlet tube extending from an opening in the top chamber portion, the outlet tube comprising a hollow lumen with a distal opening above the top chamber n for expelling the aerosol droplets, wherein the size of the hollow lumen is restricted to control the flow of the droplets or a shutter is used to control the flow of the ts, and a non-thermal plasma actuator comprising one or more electrodes adjacent to the distal opening, the electrodes configured to generate a high e pulse activating the aerosol droplets to form plasma activated ionic particles for decontaminating an article, surface, or substantially closed space. In certain embodiments, the ultrasonic cavitator is connectively linked to a ultrasonic signal generator. In ular embodiments, the ultrasonic cavitator is configured to generate aerosol droplets between 5 to 50 pm in diameter.
In another embodiment, the distal end of the ultrasonic cavitator comprises a piezoelectric disk, and the piezoelectric transducer is red to vibrate a surface of the piezoelectric disk as a e of shearing cleaning fluid. In a further embodiment, the distal end of the ultrasonic cavitator comprises a spray nozzle, and the lectric transducer is configured to vibrate a metallic surface of the nozzle as a surface of shearing cleaning fluid. In certain embodiments, the tube is connected to housing supporting a container comprising a cleaning fluid. In particular embodiments, the resonant frequency is between 25 to 200 kHz. In other embodiments, the spray nozzle produces a focused spray pattern having spray pattern between 0.07 to 1 inch in diameter. In specific embodiments, the spray nozzle produces a conical spray pattern between 2 to 6 inches in diameter. In further embodiments, the spray nozzle produces a fan-shaped spray pattern up to 12 inches wide. In another embodiment, a ity of ultrasonic spray s are disposed in the interior chamber portion. In other embodiments, the nonthermal plasma actuator ses a dielectric barrier discharge (DBD), cascaded dielectric barrier discharge, capacitative discharge, gliding arc discharge, resistive r discharge, plasma jet, pulsed spark discharge, glow discharge or a combination thereof.
In a ular embodiment, the non-thermal plasma generator is a tric DBD (VDBD) or a surface DBD (SDBD).
In certain embodiments, the power source comprises a DC power source, a high frequency AC power source, an RF power , a microwave power , a pulsed DC power source and a pulsed AC power source. In particular embodiments, the cleaning fluid comprises a liquid. In further embodiments, the cleaning fluid comprises hydrogen peroxide, peracetic acid, sodium percarbonate or a combination thereof, and optionally further the cleaning fluid comprises ents to increase free radical protection comprising ozone, alkenes, aldehydes, or halogens. In additional embodiments, the chamber is disposed within a larger r and is connected to said larger chamber by a tubular wall extending around the non-thermal plasma actuator and urally configured to allow the plasma activated ionic particles to be expelled into a subchamber in the top of the larger chamber to decontaminate at least one article placed therein. In particular embodiments, the at least one article ses a medical device or animal tissue material. In certain embodiments, the subchamber further comprises a source of sterilant gas for exposing the at least one article to the sterilant gas. In other emboduments, the sterilant gas comprises chlorine dioxide, ethylene oxide, ozone, propylene oxide, nitrogen dioxide, formaldehyde or a combination thereof. In another embodiments, the subchamber further ses means for subjecting the at least one article to ultraviolet light.
In another embodiment, the housing further comprises a movable cart, wherein the tubular wall, spray nozzle and electrodes extend from an exterior surface of the movable cart. In certain embodiments, the movable cart further comprises means for producing a sterilant gas selected from the group consisting of chlorine e, ethylene oxide, ozone, propylene oxide, nitrogen dioxide, formaldehyde or a combination f. In further embodiments, the movable cart further comprises a metal scrubber box, a blower and a carbon activated filter, and the metal er box is structurally configured so that the blower pulls air though the carbon activated filter, and a scrubber is formed by housing, blower and filter working in unison. In certain embodiments, the movable cart further comprises means for contacting the carbon activated filter with ultraviolet light in order to break down plasma activated ionic particles ng upon on the filter.
A r aspect of the application is a method for aminating an article or substantially enclosed space, comprising the steps of: submerging an ultrasonic cavitator in a reservoir of a cleaning fluid, cavitating the cleaning fluid with ultrasonic vibrations produced by the ultrasonic cavitator, ting a mist comprising aerosol droplets, wherein the mist is generated from the cleaning fluid while the cleaning fluid is being cavitated, subjecting the mist to a nonthermal plasma actuator to form plasma activated ionic les, and contacting the plasma activated ionic particles to a pathogen. In particular embodiments, the pathogen is a bacteria.
Another aspect of the ation is a method for aminating an e or substantially enclosed space, comprising the steps of: providing a reservoir of a cleaning fluid, cavitating the reservoir of cleaning fluid by applying force to the cleaning fluid; generating a mist comprising aerosol droplets, wherein the mist is generated from the cleaning fluid while the cleaning fluid is subject to cavitation by force, subjecting the mist to a nonthermal plasma or to form plasma activated ionic particles; and contacting the plasma activated ionic particles to a pathogen. In particular embodiments, the force is applied using ultrasonic vibrations. In certain embodiments, the ultrasonic vibrations are produced by an ultrasonic wafer.
Another aspect of the application is an apparatus for decontaminating an article or substantially ed space, comprising: a reservoir of cleaning fluid, an ultrasonic cavitator, n the ultrasonic cavitator is submerged in the reservoir, a rmal plasma actuator, wherein the actuator activates a mist generated from the reservoir, a funnel, wherein the funnel connects the nonthermal plasma activator to the oir, an outer tube, wherein the outer tube connects the nonthermal actuator to the external atmosphere, and wherein a mist generated from the reservoir can pass through the funnel to the actuator, and further wherein after the mist is activated by the actuator the mist can pass through the outer tube to the external atmosphere.
A further aspect of the application is a method for aminating a substantially ed space, comprising the steps of: sensing a presence of an ne pathogen in the atmosphere of a substantially enclosed space using a sensor, communicating the presence of the airborne pathogen from the sensor to a networked computer sor, communicating from the networked computer processor to a decontamination apparatus that an ne pathogen is present in the ntially enclosed space, activating a decontamination cycle of the decontamination apparatus, wherein the decontamination cycle comprises the steps of: providing a reservoir of a cleaning fluid, cavitating the reservoir of cleaning fluid by applying force to the cleaning fluid, generating a mist comprising aerosol droplets, n the mist is generated from the cleaning fluid while the cleaning fluid is subject to cavitation by force, subjecting the mist to a nonthermal plasma or to form plasma activated ionic particles, and ting the plasma activated ionic les to the airborne pathogen.
A further aspect of the ation is a system for decontaminating a substantially enclosed space, sing: a sensor for airborne pathogens, wherein the sensor is in networked communication with a computer processor, a computer processor, wherein the computer sor is in ked communication with the sensor and a decontamination apparatus, a decontamination apparatus, wherein the decontamination apparatus is in networked communication with the computer processor, and further wherein the decontamination apparatus comprises: a reservoir of cleaning fluid, an ultrasonic cavitator, wherein the ultrasonic cavitator is submerged in the reservoir, a nonthermal plasma actuator, wherein the actuator activates a mist generated from the reservoir; a funnel; n the funnel connects the nonthermal plasma tor to the reservoir; an outer tube; wherein the outer tube connects the rmal actuator to the external atmosphere; and wherein a mist ted from the reservoir can pass through the funnel to the actuator; and further wherein after the mist is activated by the or the mist can pass h the outer tube to the external atmosphere. r aspect of the application is a non-transitory computer readable medium providing instructions for repeating decontamination cycles of a decontamination apparatus; the instructions comprising: sensing a presence of a pathogen in a ntially ed space; communicating the presence of the pathogen to a computer database; fying the pathogen sensed in the substantially enclosed space using the computer database; selecting a program of amination cycles from the computer database based on the identity of the pathogen; communication the selected program to a decontamination apparatus; wherein the decontamination apparatus is ked to automatically follow the program; performing the decontamination cycles according to the program; wherein each decontamination cycle comprises the steps of: providing a reservoir of a cleaning fluid; cavitating the reservoir of cleaning fluid by applying force to the cleaning fluid; generating a mist comprising aerosol droplets; wherein the mist is generated from the cleaning fluid while the cleaning fluid is t to cavitation by force; subjecting the mist to a nonthermal plasma actuator to form plasma ted ionic les; and contacting the plasma activated ionic particles to the airborne pathogen.
A further aspect of the application is a device with an arc converter that uses pulses at a defined speed to provide better ionization.
These and other aspects and embodiments of the present application will become better understood with reference to the following detailed description when considered in association with the accompanying drawings and claims.
BRIEF DESCRIPTION OF THE DRAWINGS is a block flow diagram of a general approach for denaturing a mical agent using an activated cleaning fluid mist. is a schematic view of a first embodiment of apparatus for denaturing biological agents; with the activator proximally located to the mist generator. is a schematic view of a second embodiment of apparatus for denaturing biological agents; with the activator located remotely from the mist generator. is a schematic view of a third embodiment of apparatus for denaturing biological agents; with both proximate and remote activators. illustrates a streaming decontamination apparatus. illustrates a chamber-based decontamination apparatus. illustrates a amination apparatus for decontaminating a room.
FIG:8iflufinnesadeconMnfinafionappmanmlbraheafing,vmnflafing,andan conditioning duct system. illustrates a decontamination apparatus for air breathed by a person.
A represents a configuration of device elements wherein a cleaning fluid source 40 and a mist generator 42 are linked via an actuating device 70 that has an adjustable range of on of up to 360 degrees. B represents a configuration of device elements n a cleaning fluid source 40 is interfaced with a mist generator 42 that, in turn, is linked to a mist delivery unit 72 via an ing device 70 that has an adjustable range of rotation of up to 360 degrees. C represents a configuration of device ts wherein a mist generator 42 is mounted on an actuating device 70 that has an adjustable range of rotation of up to 360 degrees. FIG. lOD represents another configuration of device elements wherein a mist generator 42 feeds into a mist delivery unit 72 that is mounted on an actuating device 70 that has an adjustable range of rotation of up to 360 degrees.
FIG. llA depicts an embodiment wherein at least a mist generator 42 and a wfigewmw52mmmmmmdmmmammeMMmg.meflgmafimmfimmmmw cmnwamhnanfifiddhqumfi72“mmhnmybenmumedmimehmmmgormarmnmeumt FIG. llB depicts a mist generator 42 and a voltage source 52 contained within a le container, wherein the entire unit can be hand held, mounted on another apparatus, or held by/mounted on another machine or a robot. FIG. llC depicts an exemplary embodiment wherein a mist generator 42and a voltage source 52 are contained within a wearable container, such as a back pack.
A illustrates the decontamination device ses an ultrasonic wafer 78 or ultrasonic nebulizer as a mist generator. B diagrams a system wherein a mobile/wireless/remote control device 84 is functionally connected to a decontamination device of the present disclosure, such as a zer 82. C diagrams an embodiment of the system, wherein the system comprises multiple decontamination devices, such as nebulizers, that are controlled by a control device 84 and r communicate between the nebulizers 82 by wired or wireless means. Information from dual nebulizers 82 can be fed back to the l device 84 either en masse or individually. For example, the dosages emitted by two different zers 82 may start or complete at different times and the data can be reported independently.
WO 32991 FIGS. 13A-B illustrates a similar system having a single (A) or multiple (B) mist generator(s) 42 being controlled by a control device 84, which further provides data 94 to an external source regarding the treatment of an area or surface. illustrates a system wherein a mist generator 42, cleaning fluid source 40 and mist delivery unit 72 are further interfaced with a sensor 98. diagrams an exemplary rectifier for forming free radicals, comprising a voltage source 52, at least one diode/capacitor 102 interfaced with a plasma actuator 76.
Throughout the drawings, the same nce numerals and ters, unless otherwise stated are used to denote like features, elements, components or portions of the rated embodiments. Moreover, while the present disclosure will now be described in detail with reference to the figures, it is done so in connection with the illustrative ments and is not limited by the particular embodiments illustrated in the figures and appended claims.
DETAILED DESCRIPTION nce will be made in detail to certain aspects and exemplary ments of the ation, illustrating examples in the accompanying structures and figures. The s of the application are bed in conjunction with the exemplary embodiments, including methods, materials and examples, such description is non-limiting and the scope of the application is intended to encompass all equivalents, alternatives, and modifications, either generally known, or incorporated here. With respect to the teachings in the present application, any issued patent, pending patent application or patent application publication described in this application is expressly incorporated by reference herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed method and compositions belong. It must be noted that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly es otherwise. Thus, for example, reference to “a peptide” includes “one or more” peptides or a “plurality” of such peptides.
Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, r embodiment includes from the one particular value and/or to the other particular value. rly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed , and that each value is also herein disclosed as “about” that particular value in addition to the value itself.
For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that when a value is disclosed that "less than or equal to “the value,” greater than or equal to the value" and possible ranges between values are also disclosed, as appropriately understood by the skilled n. For example, if the value “ 10” is disclosed the “less than or equal to 10” as well as er than or equal to 10” is also disclosed.
As used herein, the term “decontaminating” means acting to neutralize or remove pathogens from an area or article. As used herein, the term “pathogen” includes, but is not limited to, a bacterium, yeast, protozoan, or other pathogenic microorganisms. The term “pathogen” also encompasses targeted bioterror agents.
As used , the term “bacteria” shall mean members of a large group of lular microorganisms that have cell walls but lack organelles and an organized nucleus.
Synonyms for bacteria may include the terms “microorganisms77 obes77 (L , 7 germs”, “bacilli”, and “prokaryotes.” ary bacteria include, but are not d to Mycobacterium species, ing M. tuberculosis, Staphylococcus species, including S. epidermidis, S. , and methicillin-resistant S. , Streptococcus species, including S. pneumoniae, S. pyogenes, S. mutans, S. agalactiae, S. equi, S. canis, S. bovis, S. equinus, S. anginosus, S. sanguis, S. salivarius, S. mitis, other pathogenic Streptococcal species, including Enterococcus s, such as E. faecalis and E. faecium, Haemophilus influenzae, Pseudomonas species, including P. aeruginosa, P. pseudomallei, and P. , Salmonella species, including S. enterocolitis, S. typhimurium, S. enteritidis, S. bongori, and S. choleraesuis, Shigella species, ing S. flexneri, S. sonnei, S. dysenteriae, and S. boydii, Brucella species, including B. melitensis, B. suis, B. abortus, and B. pertussis, Neisseria species, ing N. meningitidis and N. gonorrhoeae, Escherichia coli, including enterotoxigenic E. coli (ETEC), Vibrio cholerae, Helicobacter pylori, Geobacillus stearothermophilus, Chlamydia trachomatis, Clostridium difficile, Cryptococcus neoformans, Moraxella species, including M. catarrhalis, Campylobacter species, including C. jejuni, Corynebacterium species, including C. diphtheriae, C. ns, C. pseudotuberculosis, C. diphtheriticum, C. urealyticum, C. hemolyticum, C. equi, Listeria togenes, Nocardia asteroides, Bacteroides species, Actinomycetes species, Treponema pallidum, Leptospirosa species, Klebsiella pneumoniae, Proteus sp., including Proteus vulgaris, Serratia species, Acinetobacter, Yersinia species, including Y. pestis and Y. pseudotuberculosis, Francisella tularensis, Enterobacter species, iodes species, Legionella species, Borrelia burgdorferi, and the like. As used herein, the term “targeted bioterror agents” includes, but is not limited to, anthrax (Bacillus antracis), plague (Yersinia pestis), and tularemia (Franciscella tularensis).
As used herein, the term “virus” can include, but is not limited to, influenza viruses, viruses, polioviruses, noroviruses, and retroviruses. Examples of viruses include, but are not limited to, human immunodeficiency virus type 1 and type 2 (HIV-1 and HIV-2), human T-cell lymphotropic virus type I and type II (HTLV-I and HTLV-II), hepatitis A virus, hepatitis B virus (HBV), hepatitis C virus (HCV), hepatitis delta virus (HDV), hepatitis E virus (HEV), hepatitis G virus (HGV), parvovirus B19 virus, tis A virus, hepatitis G virus, hepatitis E virus, transfusion transmitted virus (TTV), Epstein-Barr virus, human cytomegalovirus type 1 (HCMV-l), human herpesvirus type 6 (HHV-6), human herpesvirus type 7 (HHV-7), human herpesvirus type 8 (HHV-S), influenza type A viruses, including subtypes HlNl and H5Nl, human metapneumovirus, severe acute atory syndrome (SARS) virus, hantavirus, and RNA viruses from Arenaviridae (e.g., Lassa fever virus (LFV)), Pneumoviridae (e.g., human metapneumovirus), Filoviridae (e.g., Ebola virus (EBOV), Marburg virus (lVfl3GV) and Zika virus); Bunyaviridae (e.g., Rift Valley fever virus (RVFV), Crimean-Congo hemorrhagic fever virus (CCHFV), and irus), Flaviviridae (West Nile virus (WNV), Dengue fever virus (DENV), yellow fever virus (YFV), GB virus C (GBV-C, formerly known as hepatitis G virus (HGV)), Rotaviridae (e.g., rotavirus), and combinations thereof. In one embodiment, the subject is infected with HIV-1 or HIV-2. As used herein, the term “fungi” shall mean any member of the group of saprophytic and parasitic spore-producing eukaryotic typically ntous organisms formerly classified as plants that lack chlorophyll and include molds, rusts, mildews, smuts, mushrooms, and yeasts. Exemplary fungi include, but are not limited to, Aspergillus species, ophytes, Blastomyces derinatitidis, Candida species, including C. albicans and Ckrusei, Malassezia furfur, Exophiala werneckii, Piedraia hortai, Trichosporon ii, Pseudallescheria boydii, lla grisea, lasma capsulatum, Sporothrix kii, Histoplasma capsulatum, Tinea species, ing T. versicolor, T. pedis T. unguium, T. cruris, T. s, T. corporis, T. barbae, Trichophyton species, including T. rubrum, T. igitale, T. tonsurans, T. violaceum, T. yaoundei, T. schoenleinii, T. megninii, T. soudanense, T. equinum, T. erinacei, and T. verrucosum, Mycoplasma genitalia, Microsporum species, ing M. audouini, M. ferrugineum, M. canis, M. nanum, M. tum, M. gypseum, M. fulvum, and the like.
As used herein, the term “protozoan” shall mean any member of a diverse group of eukaryotes that are primarily unicellular, existing singly or aggregating into colonies, are usually nonphotosynthetic, and are often classif1ed further into phyla according to their capacity for and means of ty, as by pseudopods, flagella, or cilia. Exemplary protozoans include, but are not limited to Plasmodium species, including P. falciparum, P. vivax, P. ovale, and P. malariae, Leishmania species, including L. major, L. tropica, L. donovani, L. infantum, L. chagasi, L. mexicana, L. panamensis, L. iensis and L. guyanensi, Cryptosporidium, Isospora belli, Toxoplasma gondii, Trichomonas vaginalis, and Cyclospora species.
As used herein, the term le” means any solid item or object that may be susceptible to contamination with pathogens. As used herein, the term antially enclosed space” means a room, a tent, a building, or any man-made structure that is substantially enclosed and may be susceptible to contamination with pathogens. The term “substantially enclosed space” is not limited to man-made structures, even though embodiments rated herein may be preferably directed to decontamination of such structures.
As used herein, the term “sensor” can refer to any type of sensor suitable for detecting ination on an tus, a surface, or in a substantially closed space. Examples of sensors include, but are not limited to, photosensors, voltaic sensors, weight sensors, moisture sensors, pressure sensors, or any type of biosensor.
As used , the term “shearing” refers to the process of using force to fragment liquid particles into discrete groups that move and flow as zed independent sub- groups of sheared particles until the groups of particles transition in fluid phase into a mist. As used herein, the term “mist” means a cloud of aerosol droplets. As used herein, the term “aerosol” is a colloid of fine liquid droplets of about 1 to about 20 micrometers in diameter.
As used herein, the term “cleaning fluid” refers to the source of an active species used to decontaminate an e or substantially enclosed space. The preferred active species is hydroxyl ions, and the preferred source is hydrogen de. The source may instead be a more-complex species that produces hydroxyl ions upon reaction or decomposition. Examples of such more-complex species include tic acid (CHzCOO--OH+H20), sodium percarbonate (2Na2CO3+3H202), and gluteraldehyde (CH802). The ng fluid may further include promoting species that aid the active species in accomplishing its attack upon the biological microorganisms. Examples of such promoting species e nediaminetetraacetate, isopropyl alcohol, enzymes, fatty acids, and acids. The cleaning fluid is of any operable type. The cleaning fluid must n an activatable species. A preferred cleaning fluid comprises a source of hydroxyl ions (0H) for subsequent tion.
Such a source may be hydrogen peroxide (H202) or a precursor species that produces yl ions. Other sources of hydroxyl ions may be used as appropriate. es of other operable sources of hydroxyl ions include peracetic acid (CH2COO--OH+H20), sodium percarbonate (2Na2CO3+3H202), and gluteraldehyde (CH802). Other activatable species and sources of such other activatable species may also be used.
The cleaning fluid may also contain promoting species that are not themselves sources of activatable species such as hydroxyl ions, but instead modify the decontamination reactions in some beneficial fashion. Examples include ethylenediaminetetraacetate (EDTA), which binds metal ions and allows the activated s to destroy the cell walls more readily; an alcohol such as isopropyl alcohol, which es wetting of the mist to the cells; enzymes, which speed up or intensity the redox reaction in which the activated species attacks the cell walls; fatty acids; which act as an ancillary anti-microbial and may combine with free ls to create residual anti-microbial activity; and acids such as citric acid; lactic acid; or oxalic acid; which speed up or intensity the redox reaction and may act as ary anti-microbial species to pH-sensitive organisms. Mixtures of the various activatable species and the various promoting species may be used as well. The cleaning fluids are preferably aqueous solutions; but may be ons in organics such as l. The cleaning fluid source may be a source of the cleaning fluid itself; or a source of a cleaning fluid precursor that chemically reacts or decomposes to produce the cleaning fluid.
As used herein; the term “a nonthermal plasma actuator” means an actuator that activates the cleaning fluid to an activated ion such as the ionized; plasma; or free radical states which; with the passage of time; returns to the non-activated state (a process termed “recombination”). To accomplish the activation; the activator produces activating energy such as electric energy or photonic energy. The photonic energy may be produced by a laser.
Examples of activators include an AC electric field; an AC arc; a DC electric field; a pulsed DC electric field; a DC arc; an electron beam; an ion beam; a microwave beam; a radio frequency beam; and an iolet light beam. The activator may include a tuner that tunes the amplitude; frequency; wave form; or other characteristic of the activating energy to achieve a desired; y a maximum; bination time of the activated cleaning fluid mist. As used herein; the term “plasma activated ionic particles” means activated OH' ions.
As used herein; the term “ultrasonic cavitation” means the use of ultrasonic sound to cavitate a fluid; such as a cleaning fluid. Ultrasonic cavitation can be applied to a fluid by a range of methods and devices known to one of skill in the art; including a high pressure ultrasonic nebulizer; an ultrasonic nozzle; or an ultrasonic wafer. As used herein; the term “ultrasonic” means ncies of sound above the audible range; including anything over 20kHz.
As used herein; the term “ultrasonic cavitator” means a device used to perform ultrasonic cavitation on a ng fluid. Examples of an ultrasonic cavitator include a high pressure ultrasonic nebulizer; an ultrasonic nozzle; or an ultrasonic wafer. For example; a high pressure ultrasonic nebulizer atomizes liquid particles at a pressure of 50 to 400 bar to produce aerosol droplets. An ultrasonic nozzle is a spray nozzle that uses high frequency vibration produced by piezoelectric ucers to cavitate a liquid. A preferred ment uses an onic wafer. In one embodiment the ultrasonic wafer is a ceramic diaphragm vibrating at an ultrasonic frequency to create water droplets. In another embodiment, the onic wafer is a small metal plate that vibrates at high frequency to cavitate a liquid. One of ordinary skill will understand that the choice of ultrasonic cavitator is not limiting on the scope of this application.
Method and tus for Decontamination Using an Activated Cleaning Fluid Mist As disclosed in US. Patent No. 6,969,487, which is incorporated herein by reference, a method for performing decontamination comprises the steps of producing an activated ng fluid mist n at least a portion of the cleaning fluid mist is in an activated state, and contacting the activated cleaning fluid mist to a location to be decontaminated. depicts a preferred method for ming decontamination. An activated cleaning fluid mist is produced, numeral 20. Any operable approach may be used, and a preferred approach is illustrated within step 20 of A source of a cleaning fluid is provided, numeral 22. The cleaning fluid is preferably a liquid that may be vaporized, by any means of force or energy, in ambient-pressure air to form a mist. The liquid cleaning fluid may be stored at one atmosphere or slightly greater re, while a cleaning fluid in a gaseous state usually requires pressurized storage. The source of the ng fluid may also be a precursor of the cleaning fluid, such as a solid, liquid, or gas that reacts, decomposes, or otherwise produces the cleaning fluid.
A cleaning fluid mist, containing the activatable species and the promoting species, if any, is generated, numeral 24. The mist generator to generate the cleaning fluid mist may be of any operable type. In the preferred case, the cleaning mist or vapor is fine droplets of the zed ng fluid. The droplets are preferably y uniformly sized, on the order of from about 1 to about 20 micrometers in diameter. Various types of mist generators have been used in prototype studies.
The cleaning fluid mist is activated to produce an activated cleaning fluid mist, numeral 26. The activation produces activated species of the ng fluid al in the mist, such as the cleaning fluid material in the ionized, plasma, or free l . At least a portion of the activatable species is activated, and in some cases some of the promoting species, if any, is activated. A high yield of activated species is desired to improve the efficiency of the decontamination process, but it is not necessary that all or even a majority of the activatable species achieve the activated state. Any operable activator may be used. The activator field or beam may be electrical or photonic. Examples include an AC electric field, an AC arc, a DC electric field, a pulsed DC electric field, a DC arc, an electron beam, an ion beam, a microwave beam, a radio frequency beam, and an iolet light beam produced by a laser or other source.
The activator causes at least some of the activatable species of the cleaning fluid in the cleaning fluid mist to be excited to the ion, , or free radical state, thereby achieving "activation".
These ted species enter redox reactions with the cell walls of the microbiological organisms, thereby destroying the cells or at least preventing their multiplication and growth. In the case of the red hydrogen peroxide, at least some of the H202 molecules dissociate to produce hydroxyl (OH') and monatomic oxygen (0') ionic activated species. These ted species remain dissociated for a period of time, typically several seconds or longer, during which they attack and destroy the biological microorganisms. The activator is ably tunable as to the frequency, rm, amplitude, or other properties of the activation field or beam, so that it may be optimized for achieving a maximum recombination time for action against the biological microorganisms. In the case of hydrogen peroxide, the dissociated activated species recombine to form diatomic oxygen and water, harmless molecules.
The physical onship of the mist generator and the activator may be of several types, illustrated schematically for three types of decontamination apparatus 38 in FIGS. 2-4. A source of the cleaning fluid 40 provides a flow of the cleaning fluid to a mist generator 42 in each case. The mist tor forms a cleaning fluid mist 44 of the cleaning fluid. The cleaning fluid mist 44 includes the activatable species and the promoting species, if any. In the embodiment of an activator 46, schematically illustrated as a pair of electrical discharge plates n which the cleaning fluid mist 44 passes, is located proximate to, and preferably immediately adjacent to, the mist tor 42. The mist generator 42 and the activator 46 are typically packaged together for convenience in a single housing in this case. The cleaning fluid mist 44 leaving the mist tor 42 is immediately activated by the activator 46 to produce an activated ng fluid mist 48. In the embodiment of the activator 46, here schematically illustrated as a set of microwave sources, is located remotely from the mist generator 42. The cleaning fluid mist 44 flows from mist generator 42 and remains as a non- activated cleaning fluid mist for a period of time, prior to passing into a region where it is in the influence of and activated by the activator 46. These two embodiments may be combined as shown in where the cleaning fluid mist 44 is initially activated to form the activated cleaning fluid mist 48 by an activator 46a that is proximate to the mist generator 42, and then kept in the activated state or re-activated as necessary by an activator 46b that is remote from the mist generator 42. In this case, the activator 46b is illustrated to be an ultraviolet light .
The apparatus of has the advantage that the cleaning fluid is initially activated and then maintained in an ted state for an extended period of time to e a prolonged effective state. These s types of apparatus 38 are used in differing situations according to the physical constraints of each situation, and some illustrative situations are discussed subsequently. Particle and/or gas fllters may be provided where appropriate to remove particulate matter that is the carrier for microbiological sms, and also to remove the al cleaning mist and its reaction products.
The activated cleaning fluid mist 48 is ted to ons that are to be decontaminated, numeral 28. The types of locations and the manner of contacting lead to a number of specific embodiments of the previously described general approaches, as described next. illustrates a streaming form of decontamination apparatus 38. This type of apparatus ly uses the general ration shown in where the activator 46 is located proximally to the mist generator 42. It does not require an enclosure, although it may be used within an enclosure. In and other figures illustrating specific ments of the apparatus, the common elements of structure will be given the same reference numerals as used elsewhere, and the other description is incorporated into the description of each embodiment.
Cleaning fluid from the cleaning fluid source 40 is supplied to the mist generator 42, and the cleaning fluid mist 44 flows from the mist generator 42. The ng fluid mist 44 flows through an interior of a tube 50 that channels and directs the flow of the cleaning fluid mist 44.
The activator 46 d by a voltage source 52 activates the cleaning fluid mist 44 as it flows through the interior of the tube 50, so that the activated cleaning fluid mist 48 flows from the tube 50 as a stream. The stream is ed into a volume or against an object that is to be decontaminated.
This basic configuration of may be scaled over a wide range of sizes. In one example, the cleaning fluid source 40 is a hand-held pressure can of the type commonly used to dispense fluids or gases. The voltage source 52 is a battery and a circuit to supply a high voltage to the activation source 46 for a sufficient period to activate the amount of ng fluid that is stored within the pressure can. The tube 50 is the nozzle of the re can. In another example, the tube 50 is a hand-held wand operating from a -volume cleaning fluid source 40 and with a plug-in or battery electrical voltage source 52. The cleaning fluid source 40 may be pressurized to drive the flow of the cleaning fluid through the tube 50, or there may be provided an optional pump 54 that forces the cleaning fluid h the mist generator 42 and out of the tube 50 with great force.
Other forms of the apparatus 38 are primarily used in conjunction with an enclosure, either to enclose the decontamination processing or an object or flow, or to achieve decontamination of the interior of the enclosure. illustrates the apparatus 38 including an enclosure 56 that serves as a chamber in which an object 58 is decontaminated. The object 58 may be stationary, or it may move through the enclosure 56 on a conveyer. This embodiment also illustrates the form of the present apparatus wherein the activated cleaning fluid mist 48 is added to and mixed with another gas flow 60. The activated cleaning fluid mist 48 mixes with the gas flow 60, and the mixed gas flow ts the object 58. This ment may be implemented either as a continuous-flow system, as illustrated, or as a batch system wherein the enclosure 56 is filled with the activated cleaning fluid mist 48 or with the mixture of the activated ng fluid mist 48 and the gas 60 in a batch-wise fashion.
In the embodiment of the enclosure 56 is formed by the walls, floor, and ceiling of a room or other structure such as a vehicle. The activated cleaning fluid mist is produced by an integrated apparatus of the type illustrated in in which the mist generator 42 and the activator 46a are packaged together as a single unit. An optional second tor 46b is provided and used in the manner described in relation to whose disclosure is orated here. The second tor 46b maintains the activated cleaning fluid mist in the ted state for extended periods of time, so as to allow te decontamination of the room. The second activator 46b may be built into the walls, floor, or ceiling of the enclosure 56, or they may be provided as portable units that are positioned within the enclosure 56 only during the decontamination processing. The decontamination apparatus 38 of decontaminates the interior walls of the room, vehicle, or other structure, as well as objects and people n.
An apparatus 38 of the type shown in may be used to decontaminate a room (or rooms) in a stationary home, office, or other facility, or the interior of a movable vehicle such as an aircraft, automobile, ship, or military vehicle. The enclosure 56 may also be a protective suit worn by decontamination personnel, to provide continuing decontamination of its interior for normal operation or in the event of a leak in the protective suit. illustrates an embodiment wherein the mist generator 42 and the tor 46 are built into, or temporarily inserted into, an enclosure 56 in the form of a duct of the HVAC system. The duct 62 may be part of the main duct of the HVAC system, or it may be an auxiliary duct added to the HVAC system for receiving the decontamination apparatus 38. A filter 64 is provided downstream of the mist generator 42 and activator 46 for removing particulate and any remaining mist. The filter 64 may be, for e, a porous carbon, lowrestriction cing filter of the known type.
As illustrated by the embodiment of the decontamination apparatus 38 may be used to decontaminate air and other gas flows, in addition to solid objects. illustrates an embodiment wherein the decontamination apparatus 38 is used in the manner of a gas mask to furnish decontaminated ing air for a person. The ure 56 is structured as a cannister having an air intake and an outlet providing air to a face mask 66 placed over the face of a person. The cleaning fluid mist is injected into the incoming air by the mist generator 42. The activator 46 may be positioned to activate the cleaning fluid mist in the manner of Instead, in this case the activator 46 is positioned downstream of the air intake so that the cleaning fluid mist is first thoroughly mixed with the incoming air and thereafter activated by the activator 46. The filter 64 is provided as sed earlier to remove particulate and any liquid remnants of the mist.
All of these ments in FIGS. 2-9 operate in an ambient pressure of about one atmosphere or slightly above one atmosphere, all of which are within the scope of “substantially one atmosphere ambient pressure”. As noted earlier, this capability is important because most decontamination situations require the ability to achieve the decontamination without setting up vacuum chambers or pressure chambers. The mist generator produces a small overpressure of the mist as it enters the one-atmosphere environment, but does not require either a vacuum or a pressure chamber. ally in embodiments such as those of FIGS. 3, 4, 6, 8, and 9, particulate matter may be d from the contaminated region or contaminated gas flow and collected on filters, thereby removing the carrier medium of the iological organisms as well as destroying the exposed microbiological organisms themselves.
Decontamination Method One aspect of the application relates to a method for decontaminating an article or substantially enclosed space, comprising the steps of: shearing a cleaning fluid into a mist comprising aerosol droplets accumulating in a top chamber portion of a substantially closed chamber sing a funnel shaped top chamber portion, a bottom chamber portion, a side chamber portion and an interior chamber portion, wherein the cleaning fluid is sheared by ultrasonic cavitation, subjecting the mist to a nonthermal plasma actuator to form plasma ted ionic particles, and contacting the article or substantially enclosed space to the plasma ted ionic particles. One of ordinary skill will understand that the form, such as a funnel shaped top chamber, or factor of the aerolized method of applying plasma activated ionic particles is not limiting on the invention.
Another aspect of the application s to a method for decontaminating an article or ntially enclosed space, comprising the steps of: shearing a cleaning fluid into a mist sing aerosol droplets by ting the cleaning fluid using an ultrasonic cavitator submerged in a substantially closed chamber comprising the cleaning fluid, subjecting the mist to a nonthermal plasma actuator in an outlet tube ing from an opening in a top chamber portion of the substantially closed chamber, wherein the outlet tube comprises a hollow lumen with a distal opening above the top chamber portion for ing the aerosol ts to form plasma activated ionic particles, and contacting the article or ntially enclosed space to the plasma activated ionic particles.
A further aspect of the application is a method for decontaminating an article or WO 32991 substantially enclosed space, sing the steps of: ging an onic cavitator in a reservoir of a ng fluid; cavitating the cleaning fluid with ultrasonic vibrations produced by the ultrasonic cavitator, generating a mist comprising aerosol droplets, wherein the mist is generated from the cleaning fluid while the cleaning fluid is being cavitated, subjecting the mist to a nonthermal plasma actuator to form plasma activated ionic particles; and contacting the plasma activated ionic particles to a en.
Another aspect of the application relates to a method for decontaminating an article or substantially enclosed space, comprising the steps of: providing a reservoir of a cleaning fluid, cavitating the reservoir of ng fluid by applying force to the cleaning fluid, generating a mist comprising aerosol ts, wherein the mist is generated from the cleaning fluid while the cleaning fluid is subject to cavitation by force, subjecting the mist to a nonthermal plasma or to form plasma activated ionic particles, and contacting the plasma activated ionic particles to a pathogen.
The present disclosure provides a method of decontaminating an article or substantially enclosed space by ultrasonic cavitation. The present inventors have found that the use of ultrasonic tion within the cleaning fluid unexpectedly results in a low pressure, low fluid flow mist that significantly enhances kill performance and the y to decontaminate tightly enclosed environments once the mist has been activated. The method also advantageously s the complexity of the machinery used in decontaminating processes as no air compression is required.
Decontamination Devices Another aspect of the present application relates to miniature decontamination devices that comprise a DCV miniature transformer and/or a DCV miniature compressor to reduce power demand and overall weight and size of the device. In some embodiments, a miniature decontamination device has that may be lunchbox-sized to backpack-sized, and/or has a weight in the range of 10-40 lb. In some embodiments, the miniature decontamination device is placed in a backpack, a eight portable case or on a wheeled cart. In certain embodiments, the device ses a small chamber system that heats the decontaminating solution to cause vaporization before g through the arc system. In particular embodiments, the device ses a rechargeable battery operated portable wheeled system (similar in form to an IV stand-type system).
In some embodiments, the DCV miniature transformer has an input DC voltage in the range of 6-36V and generates an output of 12-225 kV. In some embodiments, the DCV miniature transformer has an input DC voltage of 24V and generates an output of 17.5kV.
In some embodiments, the DCV miniature compressor provides a pressure in the range of 10-60 psi and has an input DC e in the range of 6-36V. In some embodiments, the DCV miniature compressor provides a pressure in the range of 30-40 psi and has an input DC voltage of 24V.
In some embodiments, the miniature decontamination device further comprises a diode/capacitor rectifier that smooth’s out arc converting process and increases the converting efficiency in AC.
In some ments, the ure decontamination device further comprises low flow pump with a flow rate in the range of 4-40 ml/min and an operating voltage in the range of 6-36VDC.
In some embodiments, the miniature decontamination device further ns a l module that allows control (e.g., start and or stop the device) and monitoring of the miniature decontaminating device from a remote device such as a tablet or a phone. In some embodiments, the control module further controls data storage, transfer and ng.
Another aspect of the present application relates to a miniature decontamination device that comprises a miniature transformer and an ultrasonic wafer or ultrasonic nebulizer as a mist generator. In some embodiments, the mist generator comprises a substantially closed sonication r that comprises a funnel shaped top r portion, a bottom chamber portion, a side chamber n and an interior chamber portion, wherein the cleaning fluid is sheared by ultrasonic cavitation within the sonication chamber. In some embodiments, the device comprises more than one ultrasonic wafer. In some further embodiments, the device comprises 2, 3, 4, 5, 6, 7,8, 9,or lO onic wafers. r aspect of the present application relates to a decontamination device that comprises a diode/capacitor rectifier that smooth’s out arc converting process and increases the converting efficiency. diagrams an exemplary rectifier comprising a voltage source 52, at least one diode/capacitor 102 interfaced with a nonthermal plasma actuator 76.
In some embodiments, the decontamination device has a modular structure that s the footprint of the device and allows exchange of modules between different s.
In some embodiments, the decontamination device further comprises low flow pump with a flow rate in the range of 4-40 ml/min and an operating voltage in the range of 6- 36VDC or 10-28 VDC.
In some embodiments, the decontamination device further contains a control module that allows control (e.g., start and or stop the device) and ring of the miniature decontaminating device from a remote device such as a tablet or a phone. In some embodiments, the control module further controls data storage, transfer and printing. In some embodiments, the control module allows for remote e and connection, for recording video or data, and for providing feedback to the manufacture during use or after use.
In some embodiments, the decontamination device is mounted on a rotating base that allows better coverage for the area to be decontaminated, as illustrated in the diagrams of FIGS. lOA-D. In some embodiments, the rotating base is a 180-degree rotating base. In some embodiments, the rotating base is a 360-degree rotating base. In some embodiments, the rotating base is an adjustable rotating base having a on range of 60-360 degrees. In some embodiments, the rotation is around a single axis. In other embodiments, the rotation is around multiple axes. In still other embodiments, the rotation is in all directions or is a fully spherical motion. FIG. lOA ents a configuration of device elements wherein a cleaning fluid source 40 and a mist generator 42 are linked via an actuating device 70 that has an adjustable range of rotation of up to 360 degrees. B represents a configuration of device elements wherein a cleaning fluid source 40 is interfaced with a mist generator 42 that, in turn, is linked to a mist delivery unit 72 via an actuating device 70 that has an able range of rotation of up to 360 degrees. FIG. lOC represents a configuration of device elements n a mist generator 42 is mounted on an actuating device 70 that has an able range of rotation of up to 360 degrees.
FIG. lOD represents another configuration of device elements wherein a mist generator 42 feeds into a mist delivery unit 72 that is d on an actuating device 70 that has an adjustable range of on of up to 360 degrees.
FIGS. llA-C depict exemplary embodiments of the decontamination device that are mobile or le. The depictions are not intended to show the elements of the device in a fixed position within the le units, rather the placement of individual ents as show is merely exemplary and the positions of the elements can be rearranged to suit a particular application. FIG. llA depicts an embodiment wherein at least a mist tor 42 and a voltage source 52 are contained within a portable housing. In some embodiments, the e source 52 is AC. In other embodiments, the e source 52 is DC. In still other embodiments, the voltage source 52 can be switched between AC and DC. The mist generator 42 is functionally connected to a mist delivery unit 72 which may be mounted on the housing or is a remote unit.
In some embodiments, the mist delivery unit 72 is hand held, mounted on another apparatus, or held by/mounted on another machine or a robot. In some further embodiments, the robots are self-navigating and patrol an area. FIG. llB depicts a mist generator 42 and a voltage source 52 contained within a portable container, wherein the entire unit can be hand held, mounted on another apparatus, or held nted on another machine or a robot. In some embodiments, the voltage source is AC. In other embodiments, the voltage source 52 is DC. In still other embodiments, the voltage source can be switched between AC and DC. In particular embodiments, the mist is dispersed from the unit via high voltage actuation 100. In some embodiments, the high voltage actuation is persistent. In other embodiments, the high voltage actuation is ittent. In particular embodiments, the high voltage actuation s the mist and further es the droplets. FIG. llC depicts an exemplary embodiment wherein a mist generator 42 and a voltage source 52 are contained within a wearable container, such as a back pack. The mist generator 42 is functionally connected to a mist delivery unit 72 which may be mounted on the container or is a remote unit. In some embodiments, the mist delivery unit 72 is hand held, mounted on another apparatus, or held by/mounted on another machine or a robot.
As exemplified in A, in some embodiments, the decontamination device comprises an onic wafer or ultrasonic nebulizer 82 as a mist generator. In some embodiments, the mist generator 42 comprises a substantially closed tion chamber that comprises a bottom chamber portion or reservoir, a top chamber portion 74 forming a pathway between the bottom chamber portion and a plasma actuator 76, a voltage source 52, a side chamber n comprising a cleaning fluid source 40 and an interior chamber portion, wherein the cleaning fluid 80 that is dispensed into the zer 82 is sheared by ultrasonic cavitation generated by a ultrasonic cavitation device 78 within the sonication chamber. The cleaning fluid 80 is introduced into a fluid chamber or reservoir until it submerges an ultrasonic cavitator 78.
The ultrasonic tor 78 produces resonant onic waves that serve to cavitate the cleaning fluid, which produces a mist of aerosol droplets that rise from the fluid through a pathway 74.
The mist passes through an applicator head and a plasma actuator, or electrodes 76, where the particles are activated before entering the external here. In some embodiments a fan may be used to direct the flow of the mist. In certain embodiments, the device ses a rotating applicator based with a small circulating fan. In other embodiments, the device comprises a self-contained applicator that would e air compressor, fluid pump, and ormer. In some embodiments, heating ts heat the space inside to spread the nebulized mist. In some embodiments, the device comprises rotating heads or nozzles.
The pathway can take any form suitable to direct the aerosol droplets from the reservoir to the plasma actuator 76. In some embodiments, the pathway is in the form of a funnel. In other embodiments, the y may be, but is not limited to, in the form of a pipe, tube, elbow or cylinder.
In some embodiments, the plasma actuator is nonthermal. In other embodiments, the plasma actuator is thermal.
B diagrams a system wherein a mobile/wireless/remote l device 84 is functionally connected to a decontamination device of the present disclosure, such as a nebulizer 82. The functional connection can be wired or wireless. In some embodiments, a wireless connection includes, but is not limited to, radio frequency, infrared, wifl, OTH, or any other suitable means of wireless communication. In some embodiments, the control device 84 sends control instructions 86 to the nebulizer 82 via the functional tion and the nebulizer 82 send feedback data 88 to the control device 84 via the functional connection. C diagrams an embodiment of the system, wherein the system comprises multiple decontamination devices, such as nebulizers 82, that are controlled by a control device 84 and further two-way communicate 90 between the zers 82 by wired or wireless means. In some embodiments, a system can have a single l unit 84 that controls multiple nebulizers 82 that are situated in different areas of a room, and/or different rooms, and or/attached to, or aimed at, different pieces of equipment, such as a flow hood, that need to be ized/decontaminated.
FIGS. l3A-B depict a similar system having a single (A) or multiple (B) mist generator(s) 42 which two-way communicate 92, 96, being controlled by a control device 84, which further provides data 94 to an external source regarding the treatment of an area or surface. diagrams a system wherein a mist generator 42, cleaning fluid source 40 and mist delivery unit 72 are further interfaced with a sensor 98. In some embodiments, the sensor 98 detects microbes (such as bacteria, protozoan, parasites, amoebae, or viral particles), that are airborne or contaminating a e. In some embodiments, the sensor 98, upon detection of contaminants, automatically rs actuation of the system.
Another aspect of the application is directed to a decontamination apparatus comprising: a substantially closed chamber comprising a funnel shaped top r n, a bottom chamber portion, a side chamber portion and an interior chamber portion, an ultrasonic cavitator comprising a proximal end and a distal end, the proximal end being connected to the bottom chamber portion, the distal end extending into r interior, the cavitator comprising a piezoelectric transducer to vibrate a material at a resonant frequency, thereby generating a plurality of sheared fluid les, an inlet tube g into the side chamber portion, the tube configured so that a cleaning fluid can passively lie in the bottom chamber portion and submerge the distal end of the ultrasonic cavitator so that the sheared fluid les flow upward h the cleaning fluid and across the liquid-air interface, forming a mist of aerosol droplets accumulating in the top chamber portion, an outlet tube extending from an g in the top chamber portion, the outlet tube comprising a hollow lumen with a distal opening above the top chamber portion for expelling the aerosol droplets, and a nonthermal plasma actuator sing one or more electrodes adjacent to the distal opening, the electrodes configured to te a high voltage pulse activating the aerosol droplets to form plasma activated ionic particles for decontaminating an article, surface, or substantially closed space.
Some examples of embodiments using the decontamination apparatus, system, or method of the present disclosure include shipping containers. For example, a shipping container may be equipped with a amination system that can sense pathogen load within, or on surfaces of, the container. Exemplary systems can feed information about pathogen load to parties equipped to receive data. In some embodiments, a system can print or record data.
Other es of embodiments using the decontamination apparatus, system, or method of the present disclosure include import, export, travel quarantine areas or checkpoints.
In some embodiments, the system includes a walk-through space or tunnel, conveyer system, moving y or any other suitable means for moving persons or objects through the mist generated by the decontamination system.
Still other es of ments using the decontamination apparatus, , or method of the present disclosure include a vehicle. In some embodiments, the vehicle is a car, truck, bus, train, airplane, or any other form of transportation purposed for the movement of goods or passengers. In r embodiments, the vehicle is an autonomous Yet other examples of embodiments using the decontamination apparatus, system, or method of the present disclosure include space travel, space tine, or structures that do not reside on the planet earth.
Some examples of embodiments using the decontamination apparatus, system, or method of the present disclosure include food processing/preparation systems. In some ments, the system includes sensors, such as photodetectors, to activate the apparatus. In some embodiments, the system includes sensors for detecting pathogen load.
Still other examples of embodiments using the amination apparatus, system, or method of the present disclosure include self-guiding robots. For example, a self- guiding robot equipped with the decontamination system can move around a space or ty, detect contamination via a single or multiple sensors of the same or different types. A self- g robot equipped with the decontamination system can treat a contaminated surface or space until bioload is reduced.
Yet other examples of ments using the decontamination apparatus, system, or method of the present disclosure include emergency biocontamination rapid deployment chambers.
Other examples of embodiments using the decontamination apparatus, , or method of the present disclosure include farms, ranches, livestock facilities or abattoirs. As non- limiting examples, a decontamination tus or system can be installed in a poultry facility, such as chicken coops, or a dairy collection facility.
Still other examples of embodiments using the decontamination apparatus, , or method of the present disclosure include, but are not limited to, gyms, studios, ng ties, or bathrooms.
Other examples of embodiments using the decontamination apparatus, system, or method of the t disclosure include ngs with a decontamination system integrated into the building systems in order to aminate the entire building or specific area of the building. In some embodiments, the system is integrated into new construction. In other embodiments, the system is integrated into the automation or ventilation systems of an existing building. In some embodiments, a decontamination system or tus of the present disclosure is programmable or automated.
Method for Decontaminating a Substantially Enclosed Space of an Airborne Pathogen A further aspect of the application is a method for decontaminating a ntially enclosed space, comprising the steps of: sensing a presence of an airborne pathogen in the here of a substantially enclosed space using a sensor, communicating the presence of the airborne pathogen from the sensor to a ked computer processor, communicating from the ked computer processor to a decontamination apparatus that an airborne pathogen is t in the substantially enclosed space, activating a decontamination cycle of the decontamination apparatus, wherein the decontamination cycle comprises the steps of: providing a reservoir of a cleaning fluid, cavitating the reservoir of cleaning fluid by applying force to the cleaning fluid, generating a mist comprising aerosol droplets, wherein the mist is ted from the cleaning fluid while the cleaning fluid is subject to cavitation by force, subjecting the mist to a nonthermal plasma actuator to form plasma activated ionic particles, and contacting the plasma activated ionic particles to the airborne pathogen.
A System for Decontaminating a ntially Enclosed Space of an Airborne Pathogen An additional aspect of the application is a system for decontaminating a substantially enclosed space, comprising: a sensor for airborne pathogens, wherein the sensor is in networked communication with a computer processor, a computer processor, wherein the computer processor is in networked communication with the sensor and a decontamination apparatus, a decontamination apparatus, wherein the decontamination apparatus is in networked communication with the computer processor, and further wherein the decontamination apparatus comprises: a reservoir of ng fluid, an ultrasonic cavitator, wherein the ultrasonic cavitator is ged in the reservoir, a nonthermal plasma actuator, wherein the actuator activates a mist ted from the reservoir, a funnel, wherein the funnel connects the nonthermal plasma activator to the reservoir; an outer tube, wherein the outer tube ts the nonthermal actuator to the external here; and wherein a mist generated from the reservoir can pass through the funnel to the or, and further wherein after the mist is activated by the actuator the mist can pass through the outer tube to the external here.
In an exemplary embodiment, the computer system includes a memory, a processor, and, optionally, a secondary e . In some embodiments, the computer system includes a plurality of processors and is configured as a plurality of, e.g., bladed servers, or other known server conflgurations. In particular embodiments, the computer system also includes an input device, a display device, and an output device. In some embodiments, the memory includes RAM or similar types of memory. In particular embodiments, the memory stores one or more applications for execution by the processor. In some embodiments, the secondary storage device es a hard disk drive, floppy disk drive, CD-ROM or DVD drive, or other types of non-volatile data storage. In particular embodiments, the processor executes the application(s) that are stored in the memory or the secondary storage, or received from the internet or other k. In some embodiments, processing by the processor may be implemented in software, such as software modules, for execution by computers or other machines. These applications preferably include instructions executable to perform the functions and methods described above and illustrated in the Figures herein. The applications preferably e GUIs through which users may view and ct with the ation(s). In other embodiments, the system comprises remote access to control and/or view the system.
A non-transitory Computer Readable Medium for Decontaminating a Substantially Enclosed Space of a Pathogen A still r aspect of the application is a non-transitory computer readable medium providing instructions for repeating decontamination cycles of a decontamination tus, the instructions comprising: sensing a presence of a pathogen in a substantially enclosed space, communicating the presence of the en to a computer database, identifying the pathogen sensed in the substantially enclosed space using the computer database, selecting a program of decontamination cycles from the computer database based on the identity of the pathogen, communication the selected m to a decontamination apparatus, wherein the decontamination apparatus is networked to automatically follow the program, ming the amination cycles according to the program, wherein each decontamination cycle comprises the steps of: providing a reservoir of a cleaning fluid, cavitating the reservoir of cleaning fluid by applying force to the cleaning fluid, generating a mist comprising aerosol droplets, wherein the mist is generated from the cleaning fluid while the cleaning fluid is subject to cavitation by force, ting the mist to a nonthermal plasma actuator to form plasma activated ionic particles; and contacting the plasma activated ionic particles to the airborne pathogen.
The following examples are by way of illustration only and should not be considered limiting on the aspects or embodiments of the application.
Example 1.
In a first test series, identical cultures of serratia marcenscens were prepared by plating onto filter papers. One specimen was incubated for 24 hours at 30° C. in air as a control. Significant growth of the bacteria culture was observed. A second specimen was exposed to a 3 percent by volume aqueous hydrogen peroxide mist (which had not been activated) for 60 seconds in air at one atmosphere re, and thereafter incubated for 24 hours at 30° C. in air. Significant growth of the ia e was observed. A third en was exposed to a 3 percent by volume aqueous hydrogen peroxide mist, which had been activated by passage through a 10.5 kilovolt AC arc, for 60 seconds in air at one atmosphere pressure, and thereafter incubated for 24 hours at 30° C. in air at one atmosphere pressure. This specimen showed no growth of the bacteria culture, which was killed by the treatment. After this tration that the tion treatment rendered the 3 percent hydrogen peroxide mist capable of preventing growth, onal respective ens were tested using 1.5 percent, 0.75 percent, 0.3 percent, and 0 percent (“activated” water vapor only) concentration hydrogen peroxide mists for 60 seconds exposure in air at one atmosphere re, and incubated as bed. The specimens contacted by the 1.5 percent and 0.75 percent hydrogen peroxide mists showed no growth. The specimen contacted by the 0.3 percent hydrogen peroxide mist showed very slight growth. The specimen contacted by the 0 percent hydrogen de mist showed significant growth of the bacteria culture.
Example 2.
For a second and third test series, a duct-simulation structure was built. The duct-simulation structure was a pipe about 10 inches in diameter and 10 feet long, oriented vertically. The mist generator and activator were positioned at the top of the pipe, and a fan ing at about 0 cubic feet per minute gas flow was positioned at the bottom of the pipe to induce a gas flow downwardly through the pipe. Test ports were located at 1 foot, 2 feet, 4 feet, and 6 feet from the top of the pipe, and specimens to be tested were inserted at the various ports.
In the second test series, ial spore strips (each about 3/4 inch long and U4 inch wide) impregnated with about 106 spores per strip of Bacillus slearolhermophilus were placed in each of the test ports of the duct-simulation structure. After testing, the specimens were ted at 50° C for seven days. In the first test specimen series, air only (no hydrogen peroxide) was flowed over the specimens for 15 seconds. Significant growth of the bacteria culture at all test ports was observed after incubation. In the second specimen series, a 6 percent by volume hydrogen peroxide mist was generated, but not activated, and fiowed over the specimens for 15 seconds. The same significant growth of the bacteria culture at all test ports was observed as for the first test specimen series. In the third specimen series, this procedure was repeated, but the 6 percent hydrogen peroxide mist was activated by a 15 kilovolt AC arc.
No growth of the bacteria culture was observed at any of the test ports. These results for bacillus thermophilus are significant, because this ia is known to be resistant to growth control using conventional, non-activated hydrogen de treatments.
Example 3.
In the third test series, bacterial spore strips like those described above were used, except that the bacteria was us subtilis var. niger. Bacillus subtilis var. niger is a recognized proxy for Bacillus anihracis, which is in the same genus and which causes anthrax.
Because of its similarity to Bacillus anihracis, Bacillus sublilis var. niger is used in laboratory testing to study growth of anthrax and its control, without the risk of cting or spreading anthrax. In the first test specimen , air only (no hydrogen de) was fiowed over the specimens for 15 seconds. Significant growth of the ia culture was observed after incubation of ens from all ports. In the second specimen series, a 6 percent by volume hydrogen peroxide mist was generated, but not activated, and fiowed over the specimens for 15 seconds. The same significant growth of the bacteria culture was observed at all ports as for the first test specimen series. In the third specimen series, this ure was repeated, but the 6 percent hydrogen peroxide mist was activated by passage through a 15 kilovolt AC arc. No growth of the bacteria culture was observed at any of the ports. This testing established that this approach ls the growth of the anthrax proxy in the duct simulation structure.
In further testing, ultrasonic cavitation of the cleaning fluid to generate a low pressure, low air flow mist resulted in superior kill.
A 16x16x16 inch box was built for this testing, with the nozzle of the decontamination apparatus penetrating the bottom of the box in the center of the bottom panel. 6-Log biological (Geobacillus stearothermophilus) and chemical (iodine H202) indicators were placed in the center of all of the vertical panels. Biological and chemical indicators were also placed on the bottom panel of the box, immediately next to the .
Activated mist was injected into the box for one minute and allowed to dwell for five minutes.
The ical indicators were then removed from the box and incubated for 7 days. Following incubation, the biological indicators were examined and exhibited 6 log kill of the bacteria. gh a ular embodiment of the invention has been described in detail for purposes of illustration, various modifications and enhancements may be made without departing from the spirit and scope of the invention. Accordingly, the invention is not to be limited except as by the appended claims.
The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention, and it is not intended to detail all those obvious modifications and variations of it which will become apparent to the skilled worker upon g the description. It is intended, however, that all such obvious modifications and variations be included within the scope of the present invention, which is defined by the following claims. The claims are ed to cover the claimed components and steps in any sequence which is effective to meet the objectives there intended, unless the context specifically indicates the contrary.

Claims (20)

WHAT IS D IS:
1. A system for decontaminating a substantially ed space, comprising: a computer processor, n the computer processor is in networked communication with a decontamination apparatus; a decontamination apparatus, wherein the decontamination apparatus is in networked communication with the computer processor, and further n the amination apparatus comprises: a reservoir of cleaning fluid, wherein the cleaning fluid comprises a source of an active species for decontamination of a substantially enclosed space, wherein the active species is hydroxyl ions and wherein the source is hydrogen peroxide; an ultrasonic tor comprising a al end and a distal end, wherein the ultrasonic tor is submerged in the reservoir; a nonthermal plasma actuator, wherein the actuator activates a mist comprising aerosol droples generated from the reservoir at substantially one atmosphere ambient pressure; a funnel, wherein the funnel connects the nonthermal plasma actuator to the reservoir; an outer tube, wherein the outer tube connects the nonthermal actuator to the external atmosphere; and n a mist generated from the reservoir can pass through the funnel to the actuator, and further wherein after the mist is activated by the actuator to form plasma activated ionic particles carried by the aerosol droplets of the mist, n the plasma activated ionic particles are hydroxyl ions, the mist is dispersed through the outer tube to the external atmosphere.
2. The system of Claim 1, wherein the system is included in a shipping container.
3. The system of Claim 1 or Claim 2, wherein the system can print or record data.
4. The system of any one of Claims 1 to 3, wherein the system includes a walk-through space or tunnel, er system, moving y for moving persons or objects through the mist generated by the decontamination system.
5. The system of any one of Claims 1 to 4, wherein the system is included in a vehicle.
6. The system of Claim 5, wherein the vehicle is a car, truck, bus, train, or airplane purposed for the movement of goods or passengers.
7. The system of any one of Claims 1 to 6, wherein the system is included in structures used in space travel or space tine.
8. The system of any one of Claims 1 to 7, wherein the system is included in a selfguiding robot.
9. The system of any one of Claims 1 to 8, wherein the system is included in an emergency contamination rapid deployment chamber.
10. The system of any one of Claims 1 to 9, wherein the system is included in poultry facility or a dairy collection facility.
11. The system of any one of Claims 1 to 10, wherein the system is included in a bathroom.
12. The system of any one of Claims 1 to 11, wherein the system is integrated into a building in order to decontaminate the entire building or a ic area of the ng.
13. The system of Claim 2, wherein the system is integrated into automation or ventilation systems of the building.
14. The system of any one of Claims 1 to 13, wherein the system is programmable or automated.
15. The system of any one of Claims 1 to 14, wherein the system is included in a backpack.
16. A method for decontaminating a substantially enclosed space, sing the steps sensing a presence of a pathogen in the atmosphere of a ntially enclosed space using a sensor; communicating the presence of the pathogen from the sensor to a networked er processor; icating from the networked computer processor to a decontamination apparatus that a pathogen is present in the substantially enclosed space; activating a decontamination cycle of the decontamination apparatus, wherein the decontamination cycle comprises the steps of: providing a reservoir of a cleaning fluid, wherein the cleaning fluid comprises a source of an active species for amination of a substantially enclosed space, wherein the active species is hydroxyl ions and wherein the source is hydrogen peroxide; cavitating the oir of cleaning fluid by applying force to the cleaning fluid; ting a mist comprising aerosol droplets, wherein the mist is generated from the cleaning fluid while the cleaning fluid is subject to cavitation by force; subjecting the mist to a nonthermal plasma actuator to form plasma activated ionic particles, wherein the plasma activated ionic particles are hydroxyl ions; and contacting the plasma activated ionic particles to the pathogen.
17. The method of Claim 16, wherein the nonthermal plasma actuator comprises a dielectric r discharge (DBD), cascaded dielectric barrier discharge, capacitative discharge, gliding arc discharge, resistive barrier discharge, plasma jet, pulsed spark discharge, glow discharge or a combination thereof.
18. The method of Claim 17, wherein the non-thermal plasma or is a volumetric DBD (VDBD) or a surface DBD (SDBD).
19. The method of any one of Claims 16 to 18, wherein the mist comprising aerosol droplets generated from the reservoir is at substantially one atmosphere ambient pressure.
20. The method of any one of Claims 16 to 19, n the aerosol droplets are n 1 to 5 µm in diameter. 1 // l 0 Hit-i. mm m M: W E 3‘13} . )1}: % «iii: ................. “Nip! (If)! «En-.9 g WRmiQmw: N<§<$w§ mwwwxww flee: . hunting. xfifi EVE {II-5. a 52.35? gm WWW §::%:::::i N: :::§s53§§35ih fiixkwfixmmmwmm 213%). ............... ii»;:. , 32s! m\<\E&%§ . %%k 32.33 inn-.3! mam; fififi 533): aha (5535‘ flux ..=:\.W Q iizgikwsi ..................................... mmwwx$th 333:3. Km? ............... KWEWEAWWAW .:.,EE::::§ «a wxmmww awn-5i! wxxxwfifigmfiw Egg: un- ........... isnnlac QQVAQRK m ham“: 2 wmfikwwm g z MMEQQWR mkxkkwwm hwxwmmfi ..... 332:?!“ QR ’
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