Investigating the impact of chlorine dioxide in shrimp-rearing water on stomach microbiome, gill transcriptome, and infection-related mortality in shrimp.

AIMS: This study aimed to assess the effects of chlorine dioxide (ClO2) in water on whiteleg shrimp Penaeus vannamei, evaluating its impact on stomach microbiota, gill transcriptome, and pathogens. METHODS AND RESULTS: ClO2 was added to the aquarium tanks containing the shrimp. The application of ClO2 to rearing water was lethal to shrimp at concentrations above 1.2 ppm. On the other hand, most of the shrimp survived at 1.0 ppm of ClO2. Microbiome analysis showed that ClO2 administration at 1.0 ppm significantly reduced the α-diversity of bacterial community composition in the shrimp stomach, and this condition persisted for at least 7 days. Transcriptome analysis of shrimp gill revealed that ClO2 treatment caused massive change of the gene expression profile including stress response genes. However, after 7 days of the treatment, the gene expression profile was similar to that of shrimp in the untreated control group, suggesting a recovery to the normal state. This 1.0-ppm ClO2 significantly reduced shrimp mortality in artificial challenges with an AHPND-causing Vibrio parahaemolyticus and white spot syndrome virus, which were added to rearing water. CONCLUSIONS: The use of ClO2 at appropriate concentrations effectively eliminates a significant portion of the bacteria in the shrimp stomach and pathogens in the water. The results of this study provide fundamental knowledge on the disinfection of pathogens in water using ClO2 and the creation of semi germ-free shrimp, which has significantly decreased microbiome in the stomach.

The toxicity of chlorine dioxide to clownfish and its bactericidal capability to pathogenic strains of vibrio spp.

Global ornamental fish transportation ranging from hours to days can produce multiple stress factors impact fish health and cause mortality. Clownfish, particularly Amphiprion ocellaris, are among the most traded saltwater ornamental fish. Vibrio includes several pathogenic strains that affect aquatic animals. Consequently, prophylactic treatment of the water or fish is recommended. In this study, six Vibrio strains including V. alginolyticus, V. parahaemolyticus and V. harveyi isolated from sick A. ocellaris and one V. harveyi strain from a sick East Asian fourfinger threadfin (Eleutheronema rhadinum) were tested for their sensitivity to a popular disinfectant, chlorine dioxide (ClO2). The results showed that 0.25 ppm ClO2 effectively suppressed five of the seven tested Vibrio strains for 24 h; however, 0.1 ppm ClO2 is safer for A. ocellaris. Meanwhile, ClO2 2.5 ppm reduced the bacterial counts to below 3.3 × 105 CFU/mL for 24 hours. The LC50 of ClO2 for A. ocellaris was 0.87 ppm at 10 min and 0.72 ppm at 24 h post treatment. Mild changes in water quality, including dissolved oxygen (DO), temperature and pH, were recorded during the trial. More research is necessary to understand the sensitivity of various aquatic animal pathogens to ClO2 and its toxicity to different aquatic animals.

Amoebicidal effect of chlorine dioxide gas against pathogenic Naegleria fowleri and Acanthamoeba polyphaga.

The pathogenic free-living amoebae, Naegleria fowleri and Acanthamoeba polyphaga, are found in freshwater, soil, and unchlorinated or minimally chlorinated swimming pools. N. fowleri and A. polyphaga are becoming problematic as water leisure activities and drinking water are sources of infection. Chlorine dioxide (ClO2) gas is a potent disinfectant that is relatively harmless to humans at the concentration used for disinfection. In this study, we examined the amoebicidal effects of ClO2 gas on N. fowleri and A. polyphaga. These amoebae were exposed to ClO2 gas from a ready-to-use product (0.36 ppmv/h) for 12, 24, 36, and 48 h. Microscopic examination showed that the viability of N. fowleri and A. polyphaga was effectively inhibited by treatment with ClO2 gas in a time-dependent manner. The growth of N. fowleri and A. polyphaga exposed to ClO2 gas for 36 h was completely inhibited. In both cases, the mRNA levels of their respective actin genes were significantly reduced following treatment with ClO2 gas. ClO2 gas has an amoebicidal effect on N. fowleri and A. polyphaga. Therefore, ClO2 gas has been proposed as an effective agent for the prevention and control of pathogenic free-living amoeba contamination.

Oral mouthwashes for asymptomatic to mildly symptomatic adults with COVID-19 and salivary viral load: a randomized, placebo-controlled, open-label clinical trial.

BACKGROUND: Recent randomized clinical trials suggest that the effect of using cetylpyridinium chloride (CPC) mouthwashes on the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) viral load in COVID-19 patients has been inconsistent. Additionally, no clinical study has investigated the effectiveness of on-demand aqueous chlorine dioxide mouthwash against COVID-19. METHODS: We performed a randomized, placebo-controlled, open-label clinical trial to assess for any effects of using mouthwash on the salivary SARS-CoV-2 viral load among asymptomatic to mildly symptomatic adult COVID-19-positive patients. Patients were randomized to receive either 20 mL of 0.05% CPC, 10 mL of 0.01% on-demand aqueous chlorine dioxide, or 20 mL of placebo mouthwash (purified water) in a 1:1:1 ratio. The primary endpoint was the cycle threshold (Ct) values employed for SARS-CoV-2 salivary viral load estimation. We used linear mixed-effects models to assess for any effect of the mouthwashes on SARS-CoV-2 salivary viral load. RESULTS: Of a total of 96 eligible participants enrolled from November 7, 2022, to January 19, 2023, 90 were accepted for the primary analysis. The use of 0.05% CPC mouthwash was not shown to be superior to placebo in change from baseline salivary Ct value at 30 min (difference vs. placebo, 0.640; 95% confidence interval [CI], -1.425 to 2.706; P = 0.543); 2 h (difference vs. placebo, 1.158; 95% CI, -0.797 to 3.112; P = 0.246); 4 h (difference vs. placebo, 1.283; 95% CI, -0.719 to 3.285; P = 0.209); 10 h (difference vs. placebo, 0.304; 95% CI, -1.777 to 2.385; P = 0.775); or 24 h (difference vs. placebo, 0.782; 95% CI, -1.195 to 2.759; P = 0.438). The use of 0.01% on-demand aqueous chlorine dioxide mouthwash was also not shown to be superior to placebo in change from baseline salivary Ct value at 30 min (difference vs. placebo, 0.905; 95% CI, -1.079 to 2.888; P = 0.371); 2 h (difference vs. placebo, 0.709; 95% CI, -1.275 to 2.693; P = 0.483); 4 h (difference vs. placebo, 0.220; 95% CI, -1.787 to 2.226; P = 0.830); 10 h (difference vs. placebo, 0.198; 95% CI, -1.901 to 2.296; P = 0.854); or 24 h (difference vs. placebo, 0.784; 95% CI, -1.236 to 2.804; P = 0.447). CONCLUSIONS: In asymptomatic to mildly symptomatic adults with COVID-19, compared to placebo, the use of 0.05% CPC and 0.01% on-demand aqueous chlorine dioxide mouthwash did not lead to a significant reduction in SARS-CoV-2 salivary viral load. Future studies of the efficacy of CPC and on-demand aqueous chlorine dioxide mouthwash on the viral viability of SARS-CoV-2 should be conducted using different specimen types and in multiple populations and settings.

Study on the disinfection effect of chlorine dioxide disinfectant (ClO2) on dental unit waterlines and its in vitro safety evaluation.

BACKGROUND: Ensuring the safety of dental unit waterlines (DUWLs) has become a pivotal issue in dental care practices, focusing on the health implications for both patients and healthcare providers. The inherent structure and usage conditions of DUWLs contribute to the risk of biofilm formation and bacterial growth, highlighting the need for effective disinfection solutions.The quest for a disinfection method that is both safe for clinical use and effective against pathogens such as Staphylococcus aureus and Escherichia coli in DUWLs underscores the urgency of this research. MATERIALS: Chlorine dioxide disinfectants at concentrations of 5, 20, and 80 mg/L were used to treat biofilms of S. aureus and E. coli cultured in DUWLs. The disinfection effectiveness was assessed through bacterial counts and culturing. Simultaneously, human skin fibroblast cells were treated with the disinfectant to observe changes in cell morphology and cytotoxicity. Additionally, the study included corrosion tests on various metals (carbon steel, brass, stainless steel, aluminum, etc.). RESULTS: Experimental results showed that chlorine dioxide disinfectants at concentrations of 20 mg/L and 80 mg/L significantly reduced the bacterial count of S. aureus and E. coli, indicating effective disinfection. In terms of cytotoxicity, higher concentrations were more harmful to cellular safety, but even at 80 mg/L, the cytotoxicity of chlorine dioxide remained within controllable limits. Corrosion tests revealed that chlorine dioxide disinfectants had a certain corrosive effect on carbon steel and brass, and the degree of corrosion increased with the concentration of the disinfectant. CONCLUSION: After thorough research, we recommend using chlorine dioxide disinfectant at a concentration of 20 mg/L for significantly reducing bacterial biofilms in dental unit waterlines (DUWLs). This concentration also ensures satisfactory cell safety and metal corrosion resistance.

Bactericidal Mechanisms of Chlorine Dioxide against Beta-Hemolytic Streptococcus CMCC 32210.

Chlorine dioxide is a globally recognized green and efficient disinfectant. This study aims to investigate the bactericidal mechanism of chlorine dioxide using beta-hemolytic Streptococcus (BHS) CMCC 32210 as a representative strain. BHS was exposed to chlorine dioxide, the minimum bactericidal concentration (MBC) values of chlorine dioxide against BHS were determined by the checkerboard method in preparation for subsequent tests. Cell morphology was observed using electron microscopy. Protein content leakage, adenosine triphosphatase (ATPase) activity, and lipid peroxidation were determined by kits, and DNA damage was determined using agar gel electrophoresis. The concentration of chlorine dioxide during disinfection showed a linear relationship with the concentration of BHS. Scanning electron microscopy (SEM) results showed that chlorine dioxide caused significant damage to the cell walls of BHS at a concentration of 50 mg/L, but had no significant effect on Streptococcus exposed to different exposure times. Furthermore, the extracellular protein concentration increased with increasing chlorine dioxide concentration, while the total protein content remained unchanged. The activities of Na+/K+-ATPase and Ca2+/Mg2+-ATPase decreased with increasing chlorine dioxide concentration. Chlorine dioxide treatment led to significant lipid peroxidation and DNA degradation in BHS. Leakage of intracellular components indicated that chlorine dioxide damaged the cell membrane of BHS. Chlorine dioxide exposure resulted in oxidative damage to lipids and proteins, which negatively impacted the cell wall and membrane of Streptococcus. This caused increased permeability and inactivation of key enzymes (Na+/K+-ATPase and Ca2+/Mg2+-ATPase) involved in respiratory metabolism, ultimately leading to DNA degradation and bacterial death due to either content leakage or metabolic failure.

Purified Chlorine Dioxide as an Alternative to Chlorine Disinfection to Minimize Chlorate Formation During Postharvest Produce Washing.

The washwater used to wash produce within postharvest washing facilities frequently contains high chlorine concentrations to prevent pathogen cross-contamination. To address concerns regarding the formation and uptake of chlorate (ClO3-) into produce, this study evaluated whether switching to chlorine dioxide (ClO2) could reduce chlorate concentrations within the produce. Because ClO2 exhibits lower disinfectant demand than chlorine, substantially lower concentrations can be applied. However, ClO3- can form through several pathways, particularly by reactions between ClO2 and the chlorine used to generate ClO2 via reaction with chlorite (ClO2-) or chlorine that forms when ClO2 reacts with produce. This study demonstrates that purging ClO2 from the chlorine and ClO2- mixture used for its generation through a trap containing ClO2- can scavenge chlorine, substantially reducing ClO3- concentrations in ClO2 stock solutions. Addition of low concentrations of ammonia to the produce washwater further reduced ClO3- formation by binding the chlorine produced by ClO2 reactions with produce as inactive chloramines without scavenging ClO2. While chlorate concentrations in lettuce, kale, and broccoli exceeded regulatory guidelines during treatment with chlorine, ClO3- concentrations were below regulatory guidelines for each of these vegetables when treated with ClO2 together with these two purification measures. Switching to purified ClO2 also reduced the concentrations of lipid-bound oleic acid chlorohydrins and protein-bound chlorotyrosines, which are exemplars of halogenated byproducts formed from disinfectant reactions with biomolecules within produce.

Revealing the Generation of High-Valent Cobalt Species and Chlorine Dioxide in the Co3O4-Activated Chlorite Process: Insight into the Proton Enhancement Effect.

A Co3O4-activated chlorite (Co3O4/chlorite) process was developed to enable the simultaneous generation of high-valent cobalt species [Co(IV)] and ClO2 for efficient oxidation of organic contaminants. The formation of Co(IV) in the Co3O4/chlorite process was demonstrated through phenylmethyl sulfoxide (PMSO) probe and 18O-isotope-labeling tests. Both experiments and theoretical calculations revealed that chlorite activation involved oxygen atom transfer (OAT) during Co(IV) formation and proton-coupled electron transfer (PCET) in the Co(IV)-mediated ClO2 generation. Protons not only promoted the generation of Co(IV) and ClO2 by lowering the energy barrier but also strengthened the resistance of the Co3O4/chlorite process to coexisting anions, which we termed a proton enhancement effect. Although both Co(IV) and ClO2 exhibited direct oxidation of contaminants, their contributions varied with pH changes. When pH increased from 3 to 5, the deprotonation of contaminants facilitated the electrophilic attack of ClO2, while as pH increased from 5 to 8, Co(IV) gradually became the main contributor to contaminant degradation owing to its higher stability than ClO2. Moreover, ClO2- was transformed into nontoxic Cl- rather than ClO3- after the reaction, thus greatly reducing possible environmental risks. This work described a Co(IV)-involved chlorite activation process for efficient removal of organic contaminants, and a proton enhancement mechanism was revealed.

Reaction Mechanisms of Chlorine Dioxide with Phenolic Compounds─Influence of Different Substituents on Stoichiometric Ratios and Intrinsic Formation of Free Available Chlorine.

Chlorine dioxide (ClO2) is an oxidant applied in water treatment processes that is very effective for disinfection and abatement of inorganic and organic pollutants. Thereby phenol is the most important reaction partner of ClO2 in reactions of natural organic matter (NOM) and in pollutant degradation. It was previously reported that with specific reaction partners (e.g., phenol), free available chlorine (FAC) could form as another byproduct next to chlorite (ClO2-). This study investigates the impact of different functional groups attached to the aromatic ring of phenol on the formation of inorganic byproducts (i.e., FAC, ClO2-, chloride, and chlorate) and the overall reaction mechanism. The majority of the investigated compounds reacted with a 2:1 stoichiometry and formed 50% ClO2- and 50% FAC, regardless of the position and kind of the groups attached to the aromatic ring. The only functional groups strongly influencing the FAC formation in the ClO2 reaction with phenols were hydroxyl- and amino-substituents in ortho- and para-positions, causing 100% ClO2- and 0% FAC formation. Additionally, this class of compounds showed a pH-dependent stoichiometric ratio due to pH-dependent autoxidation. Overall, FAC is an important secondary oxidant in ClO2 based treatment processes. Synergetic effects in pollutant control and disinfection might be observable; however, the formation of halogenated byproducts needs to be considered as well.

In vitro antiviral activity of stabilized chlorine dioxide containing oral care products.

OBJECTIVE: To determine the in vitro antiviral activity of oral care products containing stabilized chlorine dioxide toward infectious viruses that harbor in the oral cavity. Specfically, severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2), SARS-CoV, human coronavirus (HCoV) 229E, influenza A (H3N2), rhinovirus type 14, adenovirus type 5, and herpes simplex virus (HSV) type 1 and 2 were examined. METHODS: Validated in vitro suspension virucidal assays were used. Test product was mixed with the test virus for 30, 60, or 120 s, neutralized with sodium thiosulfate, serially diluted in dilution medium in a 96-well plate and incubated in a carbon dioxide incubator for 7 days. The 50% Tissue Culture Infectious Dose per milliliter was determined. RESULTS: Two rinses, one oral spray and one fluoride toothpaste showed log reduction of severe acute respiratory syndrome coronavirus-2 ranging from 1.81 to 2.98 and of influenza A from 2.58 to 4.13, respectively, within 30 s of contact time; similar results were obtained at 60 s. Further, the Ultra Sensitive rinse showed 0.19, 0.75, 1.58, 1.75, 2.66, and 3.24 log reduction of severe acute respiratory syndrome coronavirus, human coronavirus 229E, rhinovirus type 14, adenovirus type 5, and herpes simplex virus type 1 and type 2, respectively, within 30 s of contact time. CONCLUSION: Stabilized chlorine dioxide containing CloSYS® oral care products reduced the viral load of multiple viruses within 30 s. The results warrant further investigation for potential in vivo applications.

Viability of SARS-CoV-2 on lettuce, chicken, and salmon and its inactivation by peracetic acid, ethanol, and chlorine dioxide.

Since the first SARS-CoV-2 outbreak in Wuhan, China, there has been continued concern over the link between SARS-CoV-2 transmission and food. However, there are few studies on the viability and removal of SARS-CoV-2 contaminating food. This study aimed to evaluate the viability of SARS-CoV-2 on food matrices, depending on storage temperature, and inactivate the virus contaminating food using disinfectants. Two SARS-CoV-2 strains (L and S types) were used to contaminate lettuce, chicken, and salmon, which were then stored at 20,4 and -40 °C. The half-life of SARS-CoV-2 at 20 °C was 3-7 h but increased to 24-46 h at 4 °C and exceeded 100 h at -40 °C. SARS-CoV-2 persisted longer on chicken or salmon than on lettuce. Treatment with 70% ethanol for 1 min inactivated 3.25 log reduction of SARS-CoV-2 inoculated on lettuce but not on chicken and salmon. ClO2 inactivated up to 2 log reduction of SARS-CoV-2 on foods. Peracetic acid was able to eliminate SARS-CoV-2 from all foods. The virucidal effect of all disinfectants used in this study did not differ between the two SARS-CoV-2 strains; therefore, they could also be effective against other SARS-CoV-2 variants. This study demonstrated that the viability of SARS-CoV-2 can be extended at 4 and -40 °C and peracetic acid can inactivate SARS-CoV-2 on food matrices.

Randomized noninferiority field trial evaluating a postmilking teat dip for the prevention of naturally occurring intramammary infections.

The aim of this study was to perform a positive-controlled field study under natural exposure conditions to test the efficacy of a newly developed chlorine dioxide-based postmilking teat disinfectant (experimental product, EX) for noninferiority compared with an already established chlorine dioxide-based teat disinfectant (positive control product, PC). After blocking by parity, approximately 200 Holstein cows in early to mid-lactation stages from a dairy farm near Padua, Italy, were randomly assigned to one of 2 groups. Over a 13-wk period between September and December 2021, the teats of cows were dipped with the EX or the PC after each milking. Milk samples were collected from individual quarters of enrolled cows for 13 wk to determine infection status. Teat condition was assessed at wk 1, 5, and 9. Mixed logistic regression was used to analyze the effect of treatment on the incidence of new intramammary infections. For the noninferiority analysis, the upper limit of the 95% confidence interval for the difference in new intramammary infection (NIMI) rate between the 2 treatments (EX - PC) had to be to the left of the critical value d (0.035) to conclude that EX was noninferior to PC in terms of the risk of NIMI. The results showed that the incidence of new infections in the quarters treated with EX (3.1%) was not different from that in the udder quarters treated with PC (2.6%). No overall difference was found between the treatments in terms of teat condition. As the upper limit of the 95% confidence interval of the NIMI rate difference was smaller than the predefined noninferiority limit, we concluded that the EX was noninferior compared with the PC.

Lignin Degradation via Chlorine Dioxide at Room Temperature: Chemical Groups and Structural Characterization.

Lignin degradation is an effective means of achieving the high-value application of lignin, but degradation usually requires the use of high temperatures and harsh reaction-conditions. This study describes a green, mild approach for the degradation of lignin, in which chlorine dioxide (ClO2) was used for the oxidative degradation of lignin (IL) in an acidic aqueous suspension at room temperature. The optimal process conditions were: 30 mL of ClO2 solution (2.5 mg·L-1), pH 4.5 and 3 h. The FT-IR, NMR (1H NMR, 2D-HSQC and 31P NMR), XPS and GPC analyses indicated that lignin could be degraded by ClO2 relatively well at room temperature, to form quinones and muconic acids. Additionally, DIL was reduced to substances with a high phenolic-hydroxyl (OH) content (RDIL) under the presence of NaBH4, which further confirmed the composition of DIL and which can be applied to the development of lignin-based phenolic resins, providing a reference for the further modification as well as the utilization of DIL.

Effect of Substituents on Molecular Reactivity during Lignin Oxidation by Chlorine Dioxide: A Density Functional Theory Study.

Lignin is a polymer with a complex structure. It is widely present in lignocellulosic biomass, and it has a variety of functional group substituents and linkage forms. Especially during the oxidation reaction, the positioning effect of the different substituents of the benzene ring leads to differences in lignin reactivity. The position of the benzene ring branched chain with respect to methoxy is important. The study of the effect of benzene substituents on the oxidation reaction's activity is still an unfinished task. In this study, density functional theory (DFT) and the m062x/6-311+g (d) basis set were used. Differences in the processes of phenolic oxygen intermediates formed by phenolic lignin structures (with different substituents) with chlorine dioxide during the chlorine dioxide reaction were investigated. Six phenolic lignin model species with different structures were selected. Bond energies, electrostatic potentials, atomic charges, Fukui functions and double descriptors of lignin model substances and reaction energy barriers are compared. The effects of benzene ring branched chains and methoxy on the mechanism of chlorine dioxide oxidation of lignin were revealed systematically. The results showed that the substituents with shorter branched chains and strong electron-absorbing ability were more stable. Lignin is not easily susceptible to the effects of chlorine dioxide. The substituents with longer branched chains have a significant effect on the flow of electron clouds. The results demonstrate that chlorine dioxide can affect the electron arrangement around the molecule, which directly affects the electrophilic activity of the molecule. The electron-absorbing effect of methoxy leads to a low dissociation energy of the phenolic hydroxyl group. Electrophilic reagents are more likely to attack this reaction site. In addition, the stabilizing effect of methoxy on the molecular structure of lignin was also found.

ClO2-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers.

The reaction mechanism of ClO2-mediated TEMPO oxidation was investigated by EPR spectroscopy and UV-Vis spectroscopy in the context of an alternative TEMPO sequence for cellulose fiber oxidation. Without the presence of a cellulosic substrate, a reversibility between TEMPO and its oxidation product, TEMPO+, was displayed, with an effect of the pH and reagent molar ratios. The involvement of HOCl and Cl-, formed as byproducts in the oxidation mechanism, was also evidenced. Trapping HOCl partly inhibits the reaction, whereas adding methylglucoside, a cellulose model compound, inhibits the reversibility of the reaction to TEMPO.

Generation, mechanisms, kinetics, and effects of gaseous chlorine dioxide in food preservation.

Food preservation is a critical issue in ensuring food safety and quality. Growing concern around industrial pollution of food and demand for environmentally sustainable food has led to increased interest in developing effective and eco-friendly preservation techniques. Gaseous ClO2 has gained attention for its strong oxidizing properties, high efficacy in microorganism inactivation, and potential for preserving the attributes and nutritional quality of fresh food while avoiding the formation of toxic byproducts or unacceptable levels of residues. However, the widespread use of gaseous ClO2 in the food industry is limited by several challenges. These include large-scale generation, high cost and environmental considerations, a lack of understanding of its mechanism of action, and the need for mathematical models to predict inactivation kinetics. This review aims to provide an overview of the up-to-date research and application of gaseous ClO2 . It covers preparation methods, preservation mechanisms, and kinetic models that predict the sterilizing efficacy of gaseous ClO2 under different conditions. The impacts of gaseous ClO2 on the quality attributes of fresh produce and low-moisture foods, such as seeds, sprouts, and spices, are also summarized. Overall, gaseous ClO2 is a promising preservation approach, and future studies are needed to address the challenges in large-scale generation and environmental considerations and to develop standardized protocols and databases for safe and effective use in the food industry.

Antimicrobial efficacy of sodium hypochlorite and hyper-pure chlorine dioxide in the depth of dentin tubules in vitro.

OBJECTIVES: The study aimed to compare the antibacterial effect of a novel disinfectant, hyper-pure chlorine dioxide (hClO2) to sodium hypochlorite (NaOCl) in various depths of dentin tubules. MATERIALS AND METHODS: The distal root of the extracted lower molars was infected artificially with Enterococcus faecalis. The control group was rinsed with saline, and the test groups were irrigated with either 5% NaOCl or 0.12% hClO2. The longitudinally split teeth were stained by viability stain. The coronal third of the root was scanned with a confocal laser scanning microscope. The fluorescent intensities were measured, and the percentage of dead bacteria was calculated at depths up to 950 µm along the dentin tubules. The effect of penetration depth, irrigants, and their interaction on antimicrobial efficacy was determined by the linear mixed model. RESULTS: The percentage of dead bacteria was higher both in the NaOCl (45.1 ± 2.3%, p < 0.01) and in the hClO2 (44.6 ± 3.8%, p < 0.01) irrigant groups compared to saline (23 ± 4.5%); however, there was no difference between them. The percentage of killed bacteria was not correlated with the depths in any group (p = 0.633). CONCLUSIONS: Our results suggest that the functional penetration depth of NaOCl is at least 2-3 times more than published to date. There is no difference in disinfection effectiveness along the dentin tubules between NaOCl and hClO2 until at least the measured 950 µm. However, both were only able to eradicate the intratubular bacteria partially. CLINICAL RELEVANCE: Hyper-pure ClO2 could be used as an alternative or final adjuvant irrigant in endodontic treatment.

A Novel UVA/ClO2 Advanced Oxidation Process for the Degradation of Micropollutants in Water.

Ultraviolet (UV)-based advanced oxidation processes (AOPs) are increasingly used for the degradation of micropollutants in water and wastewater. This study reports a novel UVA/chlorine dioxide (ClO2) AOP based on the photolysis of ClO2 using energy-efficient UV radiation sources in the UVA range (e.g., UVA-LEDs). 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.

Photolysis of Chlorine Dioxide under UVA Irradiation: Radical Formation, Application in Treating Micropollutants, Formation of Disinfection Byproducts, and Toxicity under Scenarios Relevant to Potable Reuse and Drinking Water.

Conversion of potable reuse water utilities and drinking water utilities from a low-pressure UV/H2O2 (LPUV/H2O2) advanced oxidation process (AOP) to alternative AOPs in which oxidants can effectively absorb photons and rapidly generate radicals has attracted great interest. Herein, we propose a novel UVA/ClO2 AOP for different water treatment scenarios because of reduced photon absorption by the background matrix and high molar absorptivity for ClO2 at UVA wavelengths. While the photolysis of ClO2 produces •Cl + O2 or •ClO + O(3P) via distinct product channels, we determined the parameters needed to accurately model the loss of oxidants and the formation of byproducts and combined a kinetic model with experimental data to determine quantum yields (Φ). Modeling incorporating the optimized Φ simultaneously predicted oxidant loss and the formation of major products -HOCl, Cl-, and ClO3-. We also systematically investigated the removal of three contaminants exhibiting different radical reactivities, the formation of 35 regulated and unregulated halogenated disinfection byproducts (DBPs), DBP-associated toxicity, and N-acetylcysteine thiol reactivity in synthetic or authentic RO permeates/surface waters treated by different AOPs. The kinetic model developed in this study was used to optimize operating conditions to control undesired products and improve contaminant removal efficiency. The results indicate that UVA/ClO2 can outperform LPUV/H2O2 in terms of electrical energy per order of contaminant degradation, disinfection byproduct formation, and toxicity indices.

Reaction of Chlorine Dioxide with Saturated Nitrogen-Containing Heterocycles and Comparison with the Micropollutant Behavior in a Real Water Matrix.

Chlorine dioxide (ClO2) is a very selective oxidant that reacts with electron-rich moieties such as activated amines and thus can degrade specific N-containing micropollutants. N-containing heterocycles (NCHs) are among the most frequent moieties of pharmaceuticals. In this study, the reactions of ClO2 with ritalinic acid and cetirizine, two abundant micropollutants, and model compounds representing their NCH moiety were investigated. The pH-dependent apparent reaction rates of all NCHs with ClO2 were measured and modeled. This model showed that neutral amines are the most important species having reaction rates between 800 and 3200 M-1 s-1, while cationic amines are not reactive. Ritalinic acid, cetirizine, and their representative model compounds showed a high stoichiometric ratio of ≈5 moles ClO2 consumption per degraded ritalinic acid and ≈4 moles ClO2 consumption per degraded cetirizine, respectively. Investigation of chlorine-containing byproducts of ClO2 showed that all investigated NCHs mostly react by electron transfer and form above 80% chlorite. The reactions of the model compounds were well comparable with cetirizine and ritalinic acid, indicating that the model compounds indeed represented the reaction centers of cetirizine and ritalinic acid. Using the calculated apparent reaction rate constants, micropollutant degradation during ClO2 treatment of surface water was predicted for ritalinic acid and cetirizine with -8 to -15% and 13 to -22% error, respectively. The results indicate that in ClO2-based treatment, piperidine-containing micropollutants such as ritalinic acid can be considered not degradable, while piperazine-containing compounds such as cetirizine can be moderately degraded. This shows that NCH model compounds could be used to predict micropollutant degradation.