Download - Henry decontamination clo2 060512
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Decontamination &
Chlorine Dioxide Gas
Dr. Henry S. Luftman Consultant – Odor Science
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Presentation • Microbes – particularly fungi • Decontamination
– Terms – Types – Decontaminants
• Chlorine Dioxide – Properties – Compared to Hydrogen Peroxide and others
• Chlorine Dioxide applications – Non-fungal – Fungal
• Review and Compare
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Microbial Agents microscopic, potential pathogens
• Prions • Bacterial endospores • Protozoan cysts • Mycobacteria • Non-enveloped (naked) viruses • Fungi and fungal spores • Vegetative bacteria • Enveloped viruses
Increasing Resistance
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• Thick-walled dormant form of some bacteria. They are among the most resistant of all microbes to: – Chemicals – UV light – Drying – Heat
• Think anthrax spores from 9-11 • Often used as a standard for validating sterilants and
high-level disinfectants
Bacterial Endospores
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Fungi • Fungi are plant-like organisms that lack
chlorophyll and do not photosynthesize. They usually live on dead tissue, but can be infectious. Examples include: Mushrooms Yeast Filamentous (mold)
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Fungi Terms
• Eukaryotic cells (nuclei, DNA) • Cell wall with glycoproteins and polysacharides
(80%) – Adds resistance to chemicals
• Requirements – Organic nutrients: decaying matter, paper or
cardboard – Moisture
• Mycoses – fungal infectious diseases
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Fungi terms (cont.) • Filamentous – molds (0.5 x 5 µm)
– Hyphae à mycelia (accumulation of cell walls) – Trichophyton – dermatology issues – Asperillus – infections. Produces aflatoxinà food
(contaminant, carcinogen) – most resistant to chemicals
– Penicillium – rubratoxins à liver and kidney disease – Stachybotys – mycotoxins à headaches, allergies, “sick building”
• Unicellular – yeasts (8-10 µm) • Spores
– Resistance > veg. mold > veg. yeast > veg. bacteria – Conidia: asexual spore – Ascospore: sexual (meiotic) spore, more resistant.
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Ascospores
Sexual Reproduction Hyphal Growth
Germination
Conidiospores
Spores
Asexual Reproduction
Mold Life
Cycle
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Vegetative Bacteria Active bacteria are called vegetative.
Examples: Staphylococcus aureus Streptococcus pyogenes Geobacillus
stearothermophilus Escherichia coli Neisseria meningitidis Salmonella spp.
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Types of Disinfection
• Chemical – our focus • Radiation – ultraviolet light • Thermal – an autoclave • Filtration – a liquid filter
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Types of Disinfectants • Sterilants can kill all microbes, spores and
viruses, given enough time. • High-Level disinfectants kill all viruses,
most fungi and vegetative cells, but they may not kill endospores reliably.
• Intermediate-Level disinfectants destroy all vegetative cells including mycobacteria, fungi, and most, but not all viruses. They cannot kill endospores.
• Low-Level (General Purpose) disinfectants destroy vegetative bacteria, except mycobacteria, fungi and enveloped viruses
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• Antiseptic – A substance that prevents or inhibits the growth of microorganisms on living tissues.
• Sanitizer – A chemical agent that kills 99.999% of a specific test bacterium in 30 seconds under specified test conditions.
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Disinfectant Active Sites
Cytoplasmic Membrane
Peroxide/Peracetic acid Chlorine dioxide
Phenolics Quats
Proteins Peroxide/Peracetic acid
Chlorine dioxide Alcohols
Aldehydes Halogens Phenolics
DNA Aldehydes
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Disinfectant Vocabulary
• Viable – capable of living
• Pathogen – microorganism capable of causing disease – Bacteria - vegetative and sporal – Virus – Fungus – vegetative and sporal – Prion
• Disinfection
– Chemical or physical inactivation of pathogenic micro-organisms on inanimate surfaces.
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Vocabulary (Continued) • Decontamination
The use of physical or chemical means to remove, inactivate, or destroy bloodborne pathogens on a surface or item to the point where they are no longer capable of transmitting infectious particles and the surface or item is render safe for handling, use, or disposal.
• Sterilization Destruction of ALL microorganisms by procedure or
exposure to chemical or physical agents, or to ionizing radiation.
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• Biocide - (germicide) Kills all living organisms, pathogenic and harmless.
• Sporicide - Destroys bacterial spores.
• Tuberculocide - Kills Mycobacterium tuberculosis
• Fungicide – Kills fungal spores.
• Bactericide – Kill pathogenic and harmless bacteria, but not necessarily spores.
-Disinfection, Sterilization and Preservation, 5th ed., Block, S.S.
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Vocabulary (Continued) • Colony Forming Unit (CFU) – single
macroscopic colony formed after introducing microorganisms into growth medium
• Biological Indicator (BI) – a monitor impregnated with microbes to test the efficacy of a decontamination event
• Log Reduction – Reduction of a microbial population by 90% – Example: Starting point 1,000,000 – 1 log 100,000 – 2 log 10,000 – 4 log 100 – 6 log 1
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Properties of Ideal Disinfectants • Broad spectrum • High efficiency • Unaffected by contaminants • Nontoxic, non-corrosive, nonflammable • Odorless • Cheap • Stable • Environmentally friendly
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What affects a disinfectant’s efficiency?
• Surface condition – Rough and/or porous surfaces will be more difficult to disinfect.
• Surface temperature – Higher temperatures will speed up disinfection rates, but it will also increase evaporation.
• Organic load – Blood, sputum, bodily fluids, media, urine, feces, etc. can protect and stabilize microorganisms. Organics may also react with the disinfectant, consuming it.
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What affects a disinfectant’s efficiency?
• Contact time – Disinfectants that evaporate quickly may require multiple applications to complete the contact time.
• Dried spills – Dried media, blood, etc. will decrease a disinfectant's efficiency. • Dirt, grease, or oils – All can protect microbes, and grease and oil can repel water-based disinfectants.
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Surface Decontamination
• Cleaning – Physically removing dirt to towels or rinse – Detergents best
• Sanitization – “Killing” viables
• Bacteria – vegetative • Viruses • Mold / Fungus • Bacteria - spores
– Alcohol, bleach, quats, phenols, peroxide, ClO2
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Space Decontamination
• Exposing a confined space to a gas or vapor with sporicidal capability
• Space can be a – Room(s) or laboratory(ies) – Building – HVAC component or system – Combination of any of the above
• Non technical space – Home – Business
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Items Within Space
• Furniture • Technical equipment • Refrigerators, freezers • Computers and other electronic devices • Sinks, showers
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Requirements for a Successful Decontamination
• Disinfection – To what degree? • Choice of disinfectant • Penetration to all surfaces (optional ?) • Penetration through HVAC system
(optional) • Temperature and humidity control • Containment of fumigant
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Requirements for a Successful Decontamination (Cont.)
• Disposal of disinfectant or residue? – Vent, isloate, clean
• Validation of disinfection – Biological indicators
• Material compatibility • Safety
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Safety
• If a decontaminant at a specified concentration can kill bacterial spores, it cannot be good for people
• Relevant Material Safety Data Sheets (MSDS’s) • Appropriate personal protective equipment for
the application • Appropriate isolation from bystanders • Monitors for residual gases
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Disinfectant Phase
• Liquid (Beach, peroxide, aqueous CD, quats, phenols, oils, alcohol, …) – Ideal for accessible surfaces – Can spray, line-of-sight decontamination
• Gas (CD, formaldehyde, hydrogen peroxide (?)) – Ideal for spaces, 3 dimensional objects – Containment?
• Aerosol – a middle ground
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When are Gas Decontaminations Needed?
• Cannot reach some surfaces with liquid or fog – Contaminated plenums – Internal surfaces within equipment sets – Porous surfaces – Unassembled ductwork and HVAC systems – Interstitial spaces – Other “hidden” spaces
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When are Gas Decontaminations Needed? (cont.)
• Bacterial endospore contamination – Difficult to maintain adequate contact time
with sporicidal liquid disinfectants – Easier to validate decon via biological
indicators • Material compatibility issues
– Liquids are wet and often corrosive – Electronics, certain metals, …
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Choice of Gas Decontaminants
• Formaldehyde Gas • Hydrogen Peroxide Vapor • Chlorine Dioxide Gas • Others
– Methyl Bromide – Green House, bad with Al – Ethylene Oxide – carcinogen, explosive – Ozone – very corrosive, unstable – Peracetic Acid Vapor – corrosive, unstable, high BP
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Formaldehyde Gas CH2OH– Issues
• “Fall-out” residue – Added clean-up time
• Carcinogen • Potential residual odor • Polymerization on cold surfaces • Deactivated by some fungi
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Hydrogen Peroxide Vapor (H2O2)
• Typically delivered by flash vaporization of aqueous peroxide mixture – The mixture is generally close to or above
saturation in air • Mechanism: oxidation • Required contact time less than
formaldehyde
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HP Vapor Issues
• Instability of HP toward decomposition – Flow pattern is critical to “beat”
decomposition rate • Decomposition may block access of
decontaminant • Condensation may cause control issues
– Heat-tracing or pre-thermal treatment
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HP Vapor Issues (cont.)
• Cellulose materials absorb or decompose – May effect decontamination or aeration
• Some material issues – nylon, cellulose, copper, lead, iron oxide, epoxy – Condensation may effect painted surfaces
• Capital equipment cost • If delivered as aerosol, line-of-sight decon
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Chlorine Dioxide (CD) Properties:
Ø Yellow-Green Gas
Ø Water Soluble
Ø Boiling Point 11oC
Ø Tri-atomic Molecule
Ø Molecular Weight 67.5
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Chlorine Dioxide Gas (ClO2)
• Mechanism: Selective oxidation (no chloridation) – alcohols, aldehydes, ketones, tertiary amines
and sulfur-containing amino acids • Generated on site via reaction:
– Cl2(g) + 2NaClO2 à 2ClO2(g) + 2NaCl – 5NaClO2 + 4H+(aq)à
4ClO2(g) + 2H2O + NaCl + 4Na+(aq) • Humidification required for sporicidal work,
65-90% RH
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Chlorine Dioxide Applications Ø National Security Issues
Ø Post office anthrax cleanup Ø Bio-terrorism
Ø Contamination elimination Ø Samonella newport contamination (16 fatalities) at University of
Pennsylvania Ø BioSafety Level applications (BSL1-2-3-4)
Ø Products and equipment entering/leaving controlled environments
Ø Experiment change Ø Food Safety and Food Spoilage Reduction Ø Fungicide after Katrina Ø Water Treatment Ø Pulp and Paper (water treatment and paper bleaching)
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Chlorine Dioxide Gas – Advantages
• Safe by-products (oxygen and salt) • No residue • Not flammable / explosive • “True gas” – no condensation issues • Reputation for use in Anthrax
decontamination
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• Is toxic – and it is an irritant to the eyes, skin and respiratory system.
• Is noncorrosive to stainless steel, and is compatible with most rubber and plastics, and is nonflammable.
• It is not stable after preparation. • Cost is more than bleach. • It can be disposed of by
dilution in the sewer.
Chlorine dioxide
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Chlorine Dioxide - Issues
• Less well-known or characterized • Mild corrosion/discoloring to cold steel,
copper, brass at high concentrations – Particularly in the presence of water
• Low PEL limit (0.1 ppm)
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Sample CD Antimicrobial Spectrum of Activity
Vegetative Bacteria: Ø Staphylococcus aureus Ø Pseudomonas aeruginosa Ø Salmonella cholerasuis Ø Mycobacterium smegmatis
Fungi: Ø Aspergillus niger Ø Candida albicans Ø Trychophyton mentagrophytes
Bacterial Spores: Ø Bacillus atropheus Ø Bacillus stearothermophilus Ø Bacillus pumilus Ø Clostridium sporogenes
Viruses: Ø Herpes simplex Type I (lipid) Ø Polio Type II (non-lipid) Ø Parvo Virus
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Environmental Technology Verification (ETV) Program
In 2002, EPA established the Building Decontamination Technology Center at Battelle. Battelle plans, coordinates, and conducts verification tests of decontamination technologies and reports the results to the community at large. Information concerning this specific environmental technology area can be found on the Internet at http://www.epa.gov/etv/centers/center9.html.
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Environmental Technology Verification (ETV) Program
Building Materials • Industrial-grade carpet (IC) • Bare wood (pine lumber) (BWD) • Glass (GS) • Decorative laminate (DL) • Galvanized metal ductwork (GM) • Painted (latex, flat) wallboard
paper (PW) • Painted (latex, semi-gloss)
concrete cinder block (PC)
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Issue Formaldehyde Gas
Hydrogen Peroxide Vapor
Chlorine Dioxide Gas
Sporocidal effectiveness + + +Effective through HEPA filters
+ + / ? +
Non Carcinogenic - + +Toxicity (TWA PEL) 0.75 ppm 1.0 ppm 0.1 ppm Humidity requirement (RH) 60-90% 30% (VHP) or
ambient (Clarus)65-90%
No residue - + + + (VHP) / + / ? (Clarus) - (with chlorine)
Method of removal Neutralizer Catalytic breakdown ScrubbingLimited development effort + - +Limited cost + - - / +Cycle Time (hr) 9 to 15 4 to 7 3 to 4
Non-corrosive +
Comparison
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Widener Large Animal ICU/NICU
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George D. Widener Large Animal Hospital,
New Bolton Center • Part of University of Pennsylvania • Largest equine hospital in U.S.
~ 6000 patients per year
• Possible Salmonella outbreak detected in March 2004 – Increased environmental surveillance – Fecal samples from all animals – Improved collection and bacteria isolation methods
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Widener Large Animal ICU/NICU
• Center quarantined in May 2004, following 16 equine fatalities
• Multi-drug resistant Salmonella Newport identified – Gram-negative, non-spore forming bacteria – No human infections noted
• Multiple attempts at surface decontamination of ICU/NICU
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Interior Views
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Biological Indicators
20 Bacillus atrophaeus 40 Geobacillus stearothermophilus 40 Salmonella Newport (109 bacteria)
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Biological Indicator Results
• G. stearothermophilus (log reduction) – 32/40 strips – no growth (>log 5.4
kill) – 7/40 – 1 CFU (log 5.4 kill) – 1/40 – 2 CFU (log 5.1 kill)
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Validation Study for Biological Safety Cabinets (BSCs)
• BSCs used to simultaneously – protect biological material inside from external
contamination – protect user and lab from biological material
being manipulated • HEPA filtration, blower(s), plenums • Found in medical, veterinary,
pharmaceutical, and biotech labs
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BSC Decontamination
• Formaldehyde gas had been the standard method for >30 yrs
• National Sanitation Foundation holds the standard for BSC maintenance
• Until 2009, only formaldehyde considered “pre-validated”
• Study to confirm similar status to CD
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NSF Biological Indicator Criteria (for each trial)
• 6 pairs of BIs – 3 pairs in downstream side of exhaust
HEPA filter (center and opposite corners) – 1 pair within positive pressure plenum – 1 pair beneath cabinet workspace – 1 pair in center of upstream (dirty) side of
down flow HEPA
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Test BI Locations
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Validation Experiments • Experimenters – Micro-Clean • BSC Manufacturer – NuAire • Location – NuAire (Plymouth, MN) • Conditions:
– 60 – 75% RH – CD amount - 0.1 g/ft3
– Exposure time – 80 min
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Preparation BI PLACEMENT
SEALED CABINET
LEAK TESTING
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Preparation
BI PLACEMENT
BI RETRIEVAL
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Results – Method 1 Repeat Study
Trial # 15 17 19 14 16 18 20 Dose 3.0 3.7 3.7 2.6 3.7 3.3 3.3
Position
1 0 0 0 0 0 0 0
2 0 0 0 0 0 0 0
3 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0
5 0 0 0 0 0 0 0
6 0 0 0 0 0 0 0
P P P P P P P 0, 1, 2 = # positive BIs out of 2
A2 -6' Console B1 – 6' Console
Dose – mg-hr/L PASS PASS
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Results
• Method successfully validated on A2 console, A2 bench top, B1 and B2 cabinets
• Chlorine dioxide added to National Sanitation Foundation protocol (2009)
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Other Large Scale CD Events
• 9-11 anthrax spore decontamnations – Hart Senate Building, Miami Media Center, NJ
Post Office • Hospital decontamination (~2008) • Multiple anti-fungal fumigations in New
Orleans following Katrina
Note: It’s all the same Chlorine Dioxide
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Published works about Chlorine Dioxide as a
Decontaminant
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Comparison of Multiple Systems for Laboratory Whole Room Fumigation
• Applied Biosafety 16 (2011) 139-157 • Alan Beswick et al., The Health and Safety
Laboratory, UK • Tested HP(3), formaldehyde, CD and ozone vs 3
bacterial spore and virus. • Tested on bench, in centrifuge, on floor, within
spill • CD at top for almost all, beating HP by more
than x100 on Mycobacterium fortuitum, particularly in spill
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Effect of CD Gas on Fungi and Mycotoxins Associated with Sick Building Syndrome
• Appl. Environ Microbiol 71 (2005) 5399 • S.C.Wilson et al, Texas Tech Univ. • Stachybotrys chartarum, Cladosporium
cladosporiodes, Penicillium chrysogenum, Chaetomium globosum
• 500 to 1000 ppm CD via dry chemicals in water • 100% inactivation of conidia (asexual spores),
90% of ascospores (sexual, meiotic). • While Stachy inactivated, remains toxic
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Inactivation of Stachybotrys chartarum grown on gypsum board using aerosolized
chemical agents.
• J. Environ. Eng. Sci. 5 (2006) 75 • Andrew Wagner et al., Univ. of Cincinnati • 10% bleach (0.6% NaOCl), thiabendazole,
0.05% CD (aq), copper(II) sulfate – 4 and 8 hr. • Only bleach and CD worked (~100%) • Aerosols delivered directly to dry wall surface –
not real world for regular building.
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Aqueous Chlorine Dioxide
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Microorganisms Treatment conditions
Log Reduction
Surfaces
E. coli L. monocytogenes
0.6 mg/l - 30 min 7.3 6.3
Green peppers (Han et al. 2000, 2001)
E. coli L. monocytogenes
4.0 mg/l – 10 min 4.8 mg/l – 10 min
5.5 4.8
Apples (Du et al. 2002a and b)
E. coli L. monocytogenes
0.6 mg/l –15 min 5.6 Strawberries (Han and Linton 2002)
Salmonella spp. E. coli
0.5-1 mg/l –10 min 3-5 Cantaloupes (Han et al.)
L. monocytogenes 0.2 mg/l - 30 min 2 Lettuce (Dlima and Linton 2002)
Efficacy of ClO2 gas treatment in reducing microorganisms
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Treated with 10 mg/l Chlorine dioxide gas for 10 min and stored for 6 weeks at 4oC
Untreated and stored for 6 weeks at 4oC
Han Y., Linton, R.H., and Nelson, P.E., Inactivation of Escherichia coli O157: H7 and Listeria monocytogenes on strawberry by chlorine dioxide gas, annual meeting of Institute of Food Technologists, Anaheim, CA, 2002.
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Non-Experimental CD/MODEC Comparison
• Both have been shown as fungicidal under laboratory conditions
• The real world is not under laboratory conditions – Surfaces are porous: Liquids and most
aerosols will not penetrate – Surfaces are not all glass: Some chemicals,
such as hydrogen peroxide, decompose on paper
– Water based decontaminants corrode
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Other CD Applications
• Janitorial sanitation • Antiseptic • Odor elimination • Produce protection • Restoration • Water purification • Insecticide • Instrument sterilization • Hospitals, Locker rooms, Restaurants • Anti-Fungal station