****!!!!****!!!!**** {ICA TriNova} "method for treating an object with chlorine dioxide gas, comprising contacting the object with chlorine dioxide gas while exposing the object to less than 1000 lux of light. The disclosed method minimizes chlorine containing residue on the surface of the object. The object can be a raw agricultural commodity (RAC) such as a raw fruit or vegetable." "Residues on the walls of each jar were quantitatively recovered by washing the walls sequentially with 4-50 mL aliquots of nanopure water and combining the aliquots with additional water to bring the total volume to 250 mL. These washings were analyzed by ion chromatography for chlorate and perchlorate ions. Based on reaction profiling of these particle mixtures, the weights of the particles provided within the TYVEK sachets were adjusted so that, upon reacting, a total of 1.6 mg of ClO2 would have been produced in each jar during the 2 hour period. " "Gas Chamber Studies Show Chlorate and Perchlorate Ions can be Minimized and in the Case of Perchlorate Eliminated when Fumigation is Performed in the Substantial Absence of Light when RACs are Present" "At 120 minutes, chlorine dioxide concentrations... fell well below expected concentrations, likely due to system leaks or to chlorine dioxide reacting with the exposure chambers themselves or with the silicone sealant used on the tanks. When tomatoes were present in the treatment chambers, chlorine dioxide gas was measurable only through 30 minutes for two replicates and through 60 minutes for one replicate. These data clearly indicate that tomatoes acted as a chlorine dioxide sink, consistent with studies using radiolabel showing the propensity for chlorine dioxide consumption by biologic materials, especially those tissues with a porous surface"

****!!!!**** "The goal was to validate a cycle that could be used to treat a pharmaceutical manufacturer’s beta-lactam [antibiotics] manufacturing equipment for the future production of non-beta-lactam compounds"

****!!!!**** {Data in tables is based on limited sources} "A review of data from Hoff (1986) indicates that the disinfection efficiency of chlorine dioxide for bacteria and viruses increases approximately 2 to 3 gold as pH increases from 7 to 9." "pg 378 Table of CT Values for Inactivation of Giardia Cysts by Chlorine Dioxide in pH 6-9" "[page 379] Table of CT Values for Inactivation of Viruses by Chlorine Dioxide in pH 6-9"

****!!!!****!!!!**** " Nearly all AZTD samples completely decontaminated • Greater than 6 LR for topsoil at 1 cm depth, 2 hour, both RH levels • 2 cm topsoil much more difficult to decon" "Aqueous ClO2 completely ineffective ( 0.5 LR) at most robust test conditions (4000 ppm, 2 hr contact Time, 4 spray applications)"

****!!!! "Adding salt to the aqueous solution used to produce sterilant allows humidity control, which improves kill of bacterial spores" "• Indicator to show ClO2 is present: • Indicator is printed on or attached to inside of pouch • Changes color on exposure to ClO2" "Reversible indicator on outside of sterilizer bag to show when unit is too cold and should be warmed for correct functioning" "To eliminate bacterial spores, it is highly desirable to control the humidity during sterilization to 70 to 95%, preferably 90 to 95%. Adding NaCl to the NaClO2 solution lowers the humidity of the gases produced from 100% to the desired range."

"purification process of purifying Philippine clams in the oxygenated state with 4 times of disinfected seawater...) was explored, and the water was changed once for 8 hours, and the purification time was 24 hours. The pilot test of the process can reduce the number of E. coli population in the Philippine Hazai intestine... and the sterilization rate reaches about 95%, the sand content is reduced from 65mg/100g to 23mg/100g, and the volatile salt-based nitrogen rises from 3.8mg/100g to 5.8mg/100g," "phenolic compounds denature proteins and make microorganisms inactive, and also different from chlorine biochlorination and inactivity. When it comes into contact with microorganisms, it releases new ecological oxygen and hypochlorous acid molecules and produces a powerful bactericidal and disinfection effect. This strong oxidation effect makes the amino acids in microorganisms oxidize and decompose, so as to inhibit their growth and kill them. Its residues water, trace chloride, carbon dioxide, organic sugar and other non-toxic and harmless substances." "According to the experimental results of Chen Youlin [2], the mass fraction of chlorine dioxide only needs to be 10× 10-6 action for 5 minutes to completely kill E. coli, mass fraction 10× 10-6 action to completely kill Staphylococcus aureus, mass fraction 100× 10-6 action 10min to kill spore bacteria, mass fraction 500× 10-6 for 2min to destroy hepatitis B virus (HBSAG); Chlorine dioxide can also have a special decomposition effect on cyanide, etc"

****!!!!****!!!!**** {List of their recommended specific chlorine dioxide concentrations and contact times for disinfection against plague/epidemic diseases}

"The results show that dimethyl trisulfide and isoprene were substantially degraded into other by-products, including methane sulfonyl chloride and sulfur dioxide, during oxidation by chlorine dioxide and ozone, respectively. In contrast, 1-bromopropane, 2,3-butanedione and 1,1,2-trichloroethane have slow reaction kinetics and did not break down completely. Degradation of dimethyl trisulfide by chlorine dioxide and ozone follows the second order kinetics with half-lives of 2.2 min and 24 min, respectively. On the other hand, isoprene follows the first order reaction kinetics with rate constants of 0.4051 min-1 and 0.02244 min-1 and half-lives of 1.73 min and 32 min for degradation using ozone and chlorine dioxide, respectively. iv The oxidative degradation of 1-bromopropane, dimethyl trisulfide, and 2,3-butanedione by chlorine dioxide were more efficient than their reactions with ozone. However, the degradation of isoprene and 1,1,2-trichloroethane showed a greater reactivity toward ozone compared to chlorine dioxide. Most of the reaction products of oxidative degradation such as acetone, ethanol, formic acid, and dimethyl ether are chemically benign. But there are also by-products such as methane sulfonyl chloride, sulfur dioxide, chloroform, and cyanogen bromide that require further toxicological study."

****!!!!****!!!!**** {Includes data table of studies of gas and liquid against specific pathogens on food} "ClO2 disinfects by oxidation through the one-electron transfer mechanism, resulting in a reduction to ClO2–...The inactivation may be reached by allowing permeability of the cell membrane by changing the configuration of lipids and protein which involve the oxidation of amino acids by the gas. The second option is due to the reaction with nucleic acid and/or protein structures... However, some research showed degradation in viral RNA, inducing genotoxicity or discontinuing replication of genome information." "At higher relative humidity, a greater reduction of pathogen population was reported. This might be explained due to the increment of the pores’ sizes in the bacteria due to swelling at high humidity, which allow penetration of the ClO2 molecule into the bacteria." "Gaseous ClO2 showed a negative impact on treated fruits and vegetables through enzymatic browning formation... is related to the deterioration of nutritional quality. However, additional treatments can be added to the gas exposure to inhibit browning..." "negative color change in spinach leaves, which occurred during storage after being exposed even to 50 ppm of gaseous ClO2. Also, treatments with higher concentrations may lead to bleaching of fruits and vegetables" "reaction rate was estimated to be... which is significantly higher than the reaction rate reported by previous researchers ... the chamber used here was stainless steel... likely increased the reaction with the walls, and created minor corrosion" "larger exposure surface area for the water in contact with the gas increased the overall decay rate" "some crevices in equipment could impact the effectiveness of the ClO2 gas treatment due to the time for gas to diffuse into the crevice" "the ClO2 gas concentration is surface area- and water volume-dependent" "Results showed an increase in the reaction rate due to water presence at different water volume and exposure surface area. After 7 days’ exposure at 3000 ppm of ClO2 gas, none of the selected plastics or elastomers showed a significance difference (p0.05) in the hardness value." "excitation wavelengths of ClO2 are near the ultraviolet and visible light... leads to dissociation into ClO + O or Cl + O2" " Further research can also be extended to determine the rate of ClO2 molecules dissolving into water, and the residuals form."

In this study, black peppercorns and cumin seeds were inoculated with a five-serotype cocktail of Salmonella or its surrogate Enterococcus faecium"

"At a ClO2 dosage of 74 μM (5.0 mg L–1 as ClO2) and a UV fluence at 47.5 mJ cm–2, the UVA365/ClO2 AOP generated a spectrum of reactive species, including chlorine oxide radicals (ClO•), chlorine atoms (Cl•), hydroxyl radicals (HO•), and ozone at a concentration of ∼10–13, ∼10–15, ∼10–14, and ∼10–7 M, respectively. A kinetic model to simulate the reactive species generation in the UVA365/ClO2 AOP was established, validated against the experimental results, and used to predict the pseudo-first-order rate constants and relative contributions of different reactive species to the degradation of 19 micropollutants in the UVA365/ClO2 AOP. Compared to the well-documented UVC254/chlorine AOP, the UVA365/ClO2 AOP produced similar levels of reactive species at similar oxidant dosages but was much less pH-dependent and required much lower energy input, with much lower formation of chloro-organic byproducts and marginal formation of chlorite and chlorate.

****!!!!****!!!!**** " In practice, based on a 10% chlorine excess compared with the stoichiometry and a 95% efficiency, 1.41 g of pure sodium chlorite and 0.61 g of chlorine will be required to produce 1 g of CℓO2." "obtained by oxidizing a solution of sodium chlorite using chlorine or hydrochloric acid" "Sodium chlorite solutions can be prepared from sodium chlorite powder. Water that has first been softened will need to be used to prevent calcium carbonate from precipitating."

"Chlorine Dioxide is introduced to the pulp in the D0 tower where it reacts for approximately 1 hour. This fi rst stage chemical reaction removes most of the lignin binding agents in the pulp without destroying the carbohydrates, which would weaken the fi nal product. pH is maintained at a fairly low value (approx 2 - 4 pH) to insure a rapid chemical reaction. A higher pH level would consume more ClO2 for a given degree of bleaching. Temperatures can vary between 45 to 85°C (113 to 185°F)."

**** (2020) " ClO2 is produced on site in concentrations of... 8 to 12 thousand parts per million (ppm)" "Fortunately, ClO2 gas is self-alerting presenting a faint odor of bleach or chlorine at 0.1 ppm levels or less, thus necessitating area evacuation or use of respiratory protection. Based on ERPG data, such low-level exposure to ClO2 gas is not life-threatening. In fact, more recent studies indicate that ClO2 gas at low levels, well below the TWA17 of 0.1 ppm, could be useful as an antimicrobial in the presence of humans to mitigate and/ or prevent viral infection and possibly other related respiratory tract infections... ClO2 gas could be used in places such as hospitals, clinics, offices, hotels, schools and airport buildings without interrupting normal activities."

"Phenols... Below pH 10, a minimum of 1.5 mg/L of chlorine dioxide oxidizes 1 mg/L of phenol to benzoquinone." "Algae... adding chlorine dioxide to the reservoir at night (to prevent decomposition of chlorine dioxide by sunlight). The algae killing action is fast enough to be effective before the sun rises. A dosage of 1 mg/L " "Sulfides - it does rapidly oxidize hydrogen sulfide to sulfates in the pH range 5-9. Between pH 5-9, a minimum of 3.36 mg/L of chlorine dioxide should be used to instantly oxidize 1 mg/L of sulfide to sulfate."

"used for two purposes in this application. First, as a chemical oxidant to oxidize the sulfides to sulfates, thus preventing the formation of colloidal sulfur or iron sulfide which can plug the well, and, second, as a biocide to kill the bacteria which produce the sulfides." "For intermittent treatment, chlorine dioxide should be applied at a shock dosage of 200 - 3000 ppm"

****!!!! {Highlights of chlorine dioxide characteristics} "ClO2 does not ionize to form weak acids (as chlorine and bromine do) in aqueous solutions. This allows ClO2 to be effective over a wide pH range. " "The criteria for disinfection, as defined by the USEPA, are as follows. ClO2 meets all of these criteria. 1. a 99.9% reduction in Giardia lamblia (3 log reduction) 2. zero lactose fermenting coliform 3. less than 10 cfu/mL non-lactose fermenting coliforms and 4. 99.99% reduction in enteric virus (4 log) concentrations." "ClO2 is shown to be an effective disinfectant at residual concentrations between 0.2 and 0.8 ppm. ClO2 penetrates the cell wall of the microorganism and disrupts metabolic functions. This is more efficient than other oxidizers that “burn” whatever they come in contact with. This allows lower effective concentrations to be used. ClO2, like ozone, is a dissolved gas that penetrates biofilm by molecular diffusion. However, unlike ozone, ClO2 is stable and soluble, allowing it to travel to the base of the film where it attacks microorganisms and attacks and loosens the biofilm at its point of attachment. Other oxidizers react mostly on the surface of the biofilm to form an oxidized layer, like charring on wood. This precludes further penetration. No biocide has proved to control biofilm better than ClO2. "

****!!!!****!!!!***** "An aqueous solution of ClO2 at 126 ppm (w/w) for 15 s was effective, and no surviving virus was detected with the hemagglutination test. ClO2 gas at 5 ppm (v/v) sustained for 1 h inactivated the virus effectively, while at 2.5 ppm for 1 h only partially inactivated the virus."

"Biological tests demonstrated that the inactivation of Nosema bombycis (N. bombycis) spores by chlorine dioxide (ClO2) occurs very fast and is highly sensitive. The lowest effective inactivation dosage and time was 15 mg/mL for 30 min. "

{Note: Click blue download button for full text} "The results showed that 200–1800 mg/L of ClO2 significantly inhibited the incidence of green mold on kumquats, mandarins, Peru’s oranges, and grapefruits caused by P. digitatum. Additionally, 200 mg/L of ClO2 significantly induced cell apoptosis of P. digitatum by increasing the fluorescence intensity of the mitochondrial membrane potential from 118 to 1225 and decreased the living cell rate from 96.8 to 6.1%. Further study demonstrated that the content of malondialdehyde and nucleic acid leakage (OD260) of P. digitatum markedly increased, and the mycelial morphology was seriously damaged with increased ClO2 concentration"

****!!!!****!!!!****!!!! "Novel Technology to Reduce Risk of Viral Transmission in Enclosed Occupied Environments and Room Disinfection in Unoccupied Spaces, METSS Corporation: ... development of a novel chlorine dioxide (ClO2) gas dispersion system under a current EPA-sponsored Phase II SBIR project...). The system design offers a safe and effective means to rapidly generate ClO2 vapor for on-site room decontamination in hospital and non-hospital settings. This technology is intended to meet the demands of health care markets committed to decontaminate porous materials and sensitive equipment in rooms or vehicles used for care or transport of Ebola-exposed patients... current COVID-19 pandemic has demonstrated a clear need for technologies aimed at occupied spaces to reduce or prevent the spread of transmissible diseases through air or contact with surfaces contaminated with infectious microdroplets." "y. During repeated trials, METSS demonstrated the efficacy of low level ClO2 against Pseudomonas aeruginosa, Staphylococcus aureus, and Klebsiella pneumoniae. Additional efficacy testing was performed using MS2 (non-enveloped) and Phi6 bacteriophage (enveloped) as surrogates to SARS-CoV-2 and other human viruses...." "Decontamination of Covid-19 Vaccine Production Facility: ...a study completed within the United States Pharmaceutical Industry alongside ClorDiSys Solutions, Inc established evidence that chlorine dioxide gas has the capacity to inactivate beta-lactams" "t to achieve a 3-log reduction of beta-lactams, an inactivation cycle consisting of a 30-minute conditioning phase at 75% relative humidity, followed by an exposure to chlorine dioxide gas of at least 7,240 ppm-hours, is required. Chlorine dioxide destroys the beta-lactam ring and inactivates the compound, in similar fashion to the manner in which penicillin-resistant organisms act" "exposing the target beta-lactam to Chlorine dioxide gas at a concentration of 5mg/L" "Outdoor Systems Trial Using Full-Scale Agricultural Equipment for Wide Area Decontamination of Bacillus anthracis Surrogate Spores": ...we exploited state-of-the-art spray application technologies and formulation chemistry used in the agricultural industry, spore germination techniques and a novel decontaminant based on the targeted release of chlorine dioxide. Spores of B. thuringiensis HD-1 cry- were employed as a surrogate for virulent B. anthracis. However, key performance attributes were validated against a range of virulent B. anthracis. Preferred formulations for decontamination were developed through laboratory, environmental chamber, windtunnel and finally full-scale outdoor trials. During outdoor trials we achieved all essential success criteria on all surface types (4-Log10 reduction on wood, steel and cement). Results using steel surfaces approached that required for desirable performance (6-Log10 reduction). Significant loss of spore viability was found by environmental exposure alone (up to 3-Log10 over 72 h). However, active decontamination was more effective (up to a further 3.6-Log10 reduction in viable spores). Pre-germination before decontamination with chlorine dioxide was not found to have a benefit." "Use of Innovative Packaging to Facilitate On-Site Treatment of Waste from a Bacillus anthracis Release Incident: ...These semi-permeable materials would allow gaseous fumigants such as chlorine dioxide (ClO2) to pass into the bags but would not allow residual spores to penetrate the walls of the bags and exit into the atmosphere. Testing is currently occurring... to assess the ability of the materials to allow ClO2 to penetrate through the bag material and... to provide sufficient concentration-time exposure of the waste inside the permeation chamber"

****!!!!****!!!!*** (2011) "degradation rate of chlorine dioxide with the same initial mass concentration decreased gradually under uv, sunlight, 254 nm uv and 400-700 nm fluorescence, respectively, and the degradation rate of chlorine dioxide with the same initial mass concentration increased with the increase of gas mass concentration when the temperature varied from 15 to 25°c. therefore, the wavelength that plays a major role in the photodegradation of chlorine dioxide is ultraviolet light near 365 nm; the temperature has little effect on its degradation rate; under sunlight exposure, the degradation rate of chlorine dioxide is proportional to the first square of mass concentration, which belongs to the primary reaction, and its half-life is not related to the initial mass concentration, only related to the reaction rate constant k, and the half-life is about 63 min."

"Our experimental results show that the oxidation process is a second order overall and a first order with respect to C1O2 and MC-RR. The activation energy of MC-RR degradation by C1O2 is 53.07 kJ/mol. The rate constant k of the action can be increased by increasing temperature and decreasing pH value and ranged from 6. 11x102 L/(mol.min) to 5.29x 102 L/(mol-min) at pH from 3.44 to 10.41 at 10 ℃. Reaction products were determined to be organic and volatile, because they could be almost removed from aqueous solution by heating for 15 min at 60 ℃. In addition, the main oxidation products have m/z values of 1072 and are identified as dihydroxy isomers of MC-RR."

"four major fungal toxins of aflatoxin B1 (AFB1), zearalenone (ZEN), vomitoxin (DON) and vormatoxin B1 (FB1) were studied, and the degradation effect of ZE in corn flour and its by-products in liquid and gaseous states was evaluated in combination with grain processing technology and cl02 use."

****!!!!**** "Influenza viruses were reduced by 99.9% by 0.5–1.0 mg/L of ClO2 in less than 5 min. Higher concentration (20 mg/L) eliminated SARS-CoV-2 from sewage. ClO2 concentrations from 0.2 to 1.0 mg/L ensured at least a 99% viral reduction of AD40, HAV, Coxsackie B5 virus, and other enteric viruses in less than 30 min. Considering bloodborne viruses, 30 mg/L of ClO2 can eliminate them in 5 min. Bloodborne viruses (HIV-1, HCV, and HBV) may be completely eliminated from medical devices and human fluids after a treatment with 30 mg/L of ClO2 for 30 min. In conclusion, ClO2 is a versatile virucidal agent suitable for different environmental matrices."

****!!!!**** "WHITE PAPERS, AND APPLICATION NOTES"

****!!!!****!!!!*** (2015) ***"A methodology is proposed for quantifying the amount of ClO2 gas needed in a package and/or treatment chamber." "The diffusion coefficient was found to be 0.129, 0.145, 0.173 cm2 s−1 at 5, 23, and 40 °C, respectively. Degradation of ClO2 gas under dark, UV-A and fluorescent lamp exposure was found to follow a first-order reaction. Degradation using a 40 W UV-A lamp was approximately four orders of magnitude larger than with a 34 W fluorescent lamp." "ClO2 gas can also be converted to chlorite and then react with oxygen changing their chemical structure, mobility, and properties" "Normally, the antimicrobial activity of gaseous ClO2 increased with a longer treatment time, especially at a low treatment temperature"