Chlorine Dioxide Generation Chemical Safety and Environmental Awareness
"What hazardous chemicals are used to generate chlorine dioxide? Most processes used today use methanol, sodium chlorate, and sulfuric acid, which are all hazardous" "Methanol is highly flammable but the flame is almost invisible in daylight. It is highly toxic if it gets absorbed through skin, ingested, or inhaled."
"Sodium chlorate is only a mild skin irritant, but small quantities (5-10 g) can be fatal if ingested." "Sulfuric acid is highly corrosive so it will cause severe chemical burns if it contacts your skin or eyes." "Chlorine dioxide storage poses a significant environmental and safety threat. There are several features needed for the safe storage of chlorine dioxide. The tank should be insulated to keep chlorine dioxide cool. An explosion relief lid on the top of the tank in case an explosion occurs. Sweep air is added to the top of the storage tank to dilute the concentration of vent gas sent to the scrubber. A floating cover in the tank can reduce the amount of ClO2 gas present at the top of the tank. This can allow higher storage concentrations which can reduce tank size, energy for generation and cooling, and the amount of steam needed in the bleach plant."
Disinfection Byproducts Analysis | Thermo Fisher Scientific - US
{Chlorine dioxide, chlorite, chlorate, etc} "Chlorine dioxide disinfection byproducts: chlorate, chlorite. Health effects: Reduced ability of red blood cells to carry O2. Anemia and nervous system effects (for infants and young children)."
(2021) {Note: More in-depth evaluation addressing cellular structure of specific areas of body contact, chemistry of surrounding body fluids, etc. would also need to be evaluated if in vitro exposures described herein were to be explored for use on or in areas of the body} "ClO2 is a small molecule with a molecular weight of 67.46, and it forms a stable radical.12 ClO2 is an oxidizer, which is reduced to chlorite ion (ClO2 -) by capturing an electron (ClO2 + e- → ClO2 -). The redox potential (Eº) is relatively high as 0.95 V, therefore does not harm the human microbiome."
Chlorine Dioxide - an overview | ScienceDirect Topics
"Toxicokinetics
Chlorine dioxide can be rapidly absorbed through the gastrointestinal tract. Peak blood concentration levels can be reached within 1 h after a single dose administered orally. It can also be slowly absorbed through shaved skin with a half absorption time of 22 h. It seems unlikely that intact chlorine dioxide is absorbed by inhalation giving its highly reactive nature; it is more likely that its derivatives can be absorbed. Chlorine dioxide is metabolized to chlorite, chlorate, and mostly chloride. Most administered chlorine dioxide and its metabolites remain in plasma followed by kidneys, lungs, stomach, intestine, liver, and spleen. About 43% of orally administered chlorine dioxide is eliminated in the urine and feces within 72 h. It is not excreted via the lungs."
The interaction of sodium chlorite with phospholipids and glutathione: a comparison of effects in vitro, in mammalian and in microbial cells
In this study the interaction of the preservative sodium chlorite with unsaturated lipids and glutathione was investigated, in comparison with peroxid…
Non‐conventional methods for the control of post‐harvest pear diseases - Mari - 2003 - Journal of Applied Microbiology - Wiley Online Library
***** "ClO2 at 10 μg ml−1 effectively reduced conidial germination of all decay fungi tested after treatment for 0·5 min. Chlorine dioxide only kills by contact, not systemically, and is effective only on exposed fungal propagules, such as those suspended in water or on the surface of fruit. It does not kill pathogens under the fruit skin or active infections. Chlorine dioxide can be difficult to use indoors because when a treated water stream is agitated or aerated, some of the ClO2 comes out of solution and enters the atmosphere. There is a permissible exposure level of 0·1 μg ml−1 in the air, but workers will respond to the odour before that level is reached. In USA, for this reason the recommended rate for indoor applications is μg ml−1 or less"
Anticancer and Antiviral Activity of Chlorine Dioxide by Its Induction of the Reactive Oxygen Species | Semantic Scholar
****!!!!*** Chlorine dioxide has been used for a disinfectant by exhibiting antimicrobial activity and is also potent to kill insect pests infesting stored grains. This study aimed to extend the usefulness of chlorine dioxide with respect to anticancer and antiviral activities. Cytotoxicity of chlorine dioxide was assessed against five different human cancer cell lines. Chlorine dioxide exhibited significant cytotoxicity against two breast cancer cell lines (MCF-7, MDA-MB-231) and three colorectal cancer cell lines (LoVo, HCT-116, SW-480). This cytotoxicity appeared to be associated with the capacity of chlorine dioxide to induce the production of reactive oxygen species (ROS). Compared to control insect cell lines, the cancer cell lines possessed much higher levels of ROS. On the other hand, a treatment of an antioxidant, vitamin E, significantly reduced the cytotoxicity, suggesting that the cytotoxicity was induced by high levels of ROS production. Chlorine dioxide exhibited antiviral activity against different viruses. A baculovirus, Autographa californica nuclear polyhedrosis virus (AcNPV), is a dsDNA insect virus and lost its viral activity to form polyhedral viral particles in response to chlorine dioxide. The antiviral activity against AcNPV was dependent on the incubation time with chlorine dioxide. Tobacco mosaic virus is a ssRNA plant virus and was reduced in its population after exposure to chlorine dioxide along with significant decrease of viral symptoms. These results indicate that chlorine dioxide possesses anticancer and antiviral activities probably due to its inducing activity of ROS production.
Chemometric analysis of the consumption of oral rinse chlorite (ClO2−) by human salivary biomolecules [page 1 version]
**** {This version of article includes very useful info on stabilized chlorine dioxide} "A range of commercially available oral rinse formulations contain the active agent sodiu m chlorite (Na+/ClO2−), which is com monly referred to as ‘ stabilised’ chlorine dioxide (ClO2●). ClO2−can be converted to active ClO2● by lower-ing the pH value of aqueous solutions containing the formeragent, a process which involves its prior protonation to form unstable chlorous acid (the pKav alue for this transformation is 2.31), which then decomposes to form ClO2● (stoichio-metrically, 0.50 of a molar equivalent of this free radical..."
Search for "PB81152381" (EFFECT OF CHLORINE DIOXIDE, CHLORITE, AND NITRITE ON MICE WITH LOW AND HIGH LEVELS OF GLUCOSE-6-PHOSPHATE DEHYDROGENASE (G6PD) IN THEIR ERYTHROCYTES) - NTIS
Chlorine dioxide oxidations of tyrosine, N-acetyltyrosine, and dopa - PubMed
2005 "The reactions of aqueous ClO2 with tyrosine, N-acetyltyrosine, and dopa (3,4-dihydroxyphenylalanine) are investigated from pH 4 to 7. The reaction rates increase greatly with pH to give a series of oxidized products."
**** {for Historical reference} "OSHA comments from the January 19, 1989 Final Rule on Air Contaminants Project extracted from 54FR2332 et. seq. This rule was remanded by the U.S. Circuit Court of Appeals and the limits are not currently in force." Rats exposed to 0.1-ppm concentrations of chlorine dioxide for 10 weeks at five hours daily showed no adverse effects from exposures. Other data in animals are not available."
Guidelines for Drinking-water Quality, Fourth Edition - chloride-chlorate-fs-new.pdf
" it is normal practice to supply water with a chlorine dioxide residual of a few tenths of a milligram per litre to act as a preservative during distribution" "The taste and odour threshold for this compound is 0.4 mg/l."
ANTIMICROBIAL EFFECT OF SLOW RELEASE CHLORINE DIOXIDE DISINFECTANT, IN COMPARISON WITH SODIUM DICHLOROISOCYANURATE ~dissertation
Aseptrol slow-release chlorine dioxide (in liquid). "30ppm chlorine dioxide to be mycobactericidal in 60 seconds and sporicidal in 1 to 5 minutes." "...this organic material did not affect the microbicidal properties of chlorine and chlorine dioxide. This is contrary to the finding of Isomoto who showed that organic material can compromise the efficacy of chlorinated compounds. " {Financial & time savings--Although manufacturers recommend daily prep, solution was found effective 27 days} "A study has shown the safety of chlorine dioxide on gingival fibroblasts (Nishikiori et al., 2008)"
The Science of Chlorine Dioxide | Frontier Pharmaceutical, Inc.
****!!!**** "Because animal cells do not have cell "walls", as do microorganisms, human tissue is not affected by the same action" Chlorine dioxide is a friendly compound used to disinfect meat, seafood, fruit and surfaces, whiten teeth, eliminate Mouth odor, and treat wounds and infections" "The generation of chlorine dioxide is immediate, and the resulting product is highly suited for topical applications. The DioxiCare System separates Frontier's products from other chlorine dioxide preparations. " "Chlorine dioxide deactivates microorganisms by breaking the bacterial cell wall, or, in the case of viruses, by loosening the viral envelope. This action occurs immediately upon exposure." "Studies show that DioxiCare is an outstanding promoter of wound healing, and has successfully treated many skin diseases. In addition to antimicrobial properties, the DioxiCare System likely oxidizes and neutralizes free radicals and cytokines - the irritating compounds released by the body in response to injury or disease."
Treatment of Drinking Water With Chlorine Dioxide (ClO2) ~Vulcan Chemicals
*****!!!**** {Includes graphs of bactericidal effects at different temperatures and pH} "Chlorine dioxide reacts primarily by oxidation; however, chlorine reacts by both oxidation and electrophilic substitution to yield volatile and nonvolatile chlorinated organic substances (THMs)." "1.34 lb of pure sodium chlorite will react with 0.5 lb of chlorine to produce 1.0 lb of chlorine dioxide. However, since dry technical sodium chlorite is 80% active, the reaction takes 1.68 lb of technical sodium chlorite. Usually a slight excess of chlorine should be used to insure that the reaction solution has a pH value between 2-4. This will produce chlorine dioxide more efficiently" "chlorine dioxidecan also be prepared by mixing sodium hypochlorite bleaching solution with sodium chlorite and an acid... The reaction with sulfuric acid as shown... produces the highest purity chlorine dioxide. Other inorganic and organic acids may be used and hydrochloric acid reportedly produces the most efficient generation of chlorine dioxide." "Sodium chlorite may cause anemia by oral exposure and has low toxicity by dermal exposure. Dry sodium chlorite has an oral LD50 (rat) of 165 mg/kg and sodium chlorite solutions have an oral LD50 (rat) of 350 mg/kg. Sodium chlorite dry and solution products have a dermal LD50 (rabbit) of greater than 2 g/kg." "Sodium chlorite, dry, is a fire or explosion hazard when contaminated with combustible material... Sodium chlorite, solution, also becomes a fire or explosion hazard if allowed to dry and can ignite... Continue to keep damp."
Overall view of ClO2 by Howard Alliger (Frontier Pharmaceutical)
****!!!!**** "The method of chlorine dioxide bacterial kill at low ppm concentration seems to occur by the disruption of protein synthesis and enzyme inactivation.48 49 This is similar to the "time honored", non-toxic mechanism of some common antibiotics. Oxidation of RNA and DNA do not appear to take place, or are at least unimportant in the process. The site of action lies in the soluble fraction of the cell and there appears to be no damage to whole structural components such as ribosomes" "At high ClO2 ppm, the method of rapid bacterial and viral kill appears to be the softening and destroying of the cell wall or viral capsid.52 Human cells do not have similar cell walls and are apparently unaffected. Our skin and bodies are likely protected from the general oxidative effects of ClO2 by the many reducing agents in our cells and blood, such as catalase, glutathione, superoxide dismutase, vitamins E, C, A, B complex, uric acid, zinc and selenium. This is probably the same internal protective mechanism that prevents damage from oxygen and free radicals. Bacteria and viruses do not contain most of these reducing compounds. Because ClO2 is a strong oxidizing agent and also itself a free radical, it quickly neutralizes reactive molecules,such as ****cytokines**** and oxygen free-radicals such as NO•, O2¯, H2O2, HClO, and OH •that are produced in the body by macrophages. These oxygen compounds are released in response to stress or infection and cause inflammation and pain. Other potential irritants found in wounds are similarly oxidized or reduced, such as leukotrienes, TNF, and interleukin. This neutralizing property of ClO2, combined with its ability to completely disinfect, makes IOXIDERM and DIOXIGUARD ideal wound medications. Unlike iodine compounds, or chlorhexidine, healing is not impeded.53 54 Veterinarians have been treating deep wounds and abscesses on tigers and elephants as well as dogs and cats with outstanding success.55 DIOXIDERM GEL had similar striking results on human (otherwise non-healing) diabetic ulcers." "The NOAEL, from animal ingestion studies involving ClO2 and ClO2 ̄, ranges to 100 ppmv[???] about the concentration of Frontier's DioxiDerm gel for topical use. . Water solutions of ClO2 will remain stable for several months if stored in a glass or PET bottle. “Stabilized” chlorine dioxide, which is a buffered solution ofsodium chlorite, does not release ClO2 until the pH of the solution is brought below 3." "Many nutrition and toxicology studies have been performed assessing chlorine dioxide's effect on flour. Treatment of flour with 200 ppm, fed to rats, had no effect after several generations.24,25 Flour treated with up to 500 ppm (5 times the concentration in DioxiCure Gel) fed to puppies had no untoward effect.26 Thirteen human subjects fed experimentally for six weeks with flour products that were treated with doses up to 400 ppm had no detectable toxic symptoms.27 Flour bleached with normal dosage is not reduced appreciably in nutritive value.28 Essential fatty acids are generally not effected, but tocopherol and cystine are oxidized." "hippuric acid, cinnamic acid, betaine, creatine, alanine, phenylalanine, valine, leucine, asparaginic acid, asparagine, glutaminic acid, serine, hydroxyproline, taurine, ... HO groups in alcohols and HO acids"
Chlorine Dioxide (CLO2) As a Non-Toxic Antimicrobial Agent for Virus, Bacteria and Yeast (Candida Albicans)
{A number of statements in this document need verification. Author has non-traditional background.} "The use of a family of chemical agents, releasing active species of oxygen, effective against infectious microorganisms and viruses is described with emphasis on Chlorine Dioxide (CLO2), one of the oxides of chlorine. " "Explanation of the biochemical mechanisms of acid of CLO2 as an anti-microbial agent, is presented. Particular attention is given to Candida albicans, cytomegalovirus, polio virus, Herpes I and II, HTLV-III and Pseudomonas responding to the clinical application of CLO2. It is implied that these biochemical mechanisms are so fundamental that the development of resistant strains of bacteria and/or yeast would not occur with other anti-infectious agents. Limited lists of health abnormalities that respond to CLO2 are discussed."