Prediction of Photolysis Kinetics of Viral Genomes under UV254 Irradiation to Estimate Virus Infectivity Loss.

UV254 irradiation disinfection is a commonly used method to inactivate pathogenic viruses in water and wastewater treatment. Model prediction method can serve as a pre-screening tool to quickly estimate the effectiveness of UV254 irradiation on emerging or unculturable viruses. In this study, an improved prediction model was applied to estimate UV254 photolysis kinetics of viral genomes (kpred, genome) based on the genome sequences and their photoreactivity and to correlate with the experimental virus infectivity loss kinetics (kexp, infectivity). The UV254 inactivation data of 102 viruses (including 2 dsRNA, 65 ssRNA, 33 dsDNA and 2 ssDNA viruses) were collected from the published experimental data with kexp, infectivity ranging from 0.016 to 3.49 cm2 mJ-1. The model had fairly good performance in predicting the virus susceptibility to UV254 irradiation except dsRNA viruses (Pearson's correlation coefficient = 0.64) and 70% of kpred, genome fell in the range of 1/2 to 2 times of kexp, infectivity. The positive deviation of the model often occurred for photoresistant viruses with low kexp, infectivity less than 0.20 cm2 mJ-1 (e.g., Adenovirus, Papovaviridae and Retroviridae). We also applied this model to predict the UV254 inactivation rate of SARS-CoV-2 (kpred, genome = 3.168 cm2 mJ-1) and a UV dose of 3 mJ cm-2 seemed to be able to achieve a 2-log removal by conservative calculation using 1/2kpred, genome value. This prediction method can be used as a prescreening tool to assess the effectiveness of UV254 irradiation for emerging/unculturable viruses in water or wastewater treatment.

Both viable and inactivated amoeba spores protect their intracellular bacteria from drinking water disinfection.

In drinking water systems, waterborne pathogens constitute a significant threat. While most studies focus on a single infectious agent, such as bacteria, fungi, viruses, and protists, the effect of interactions among these infectious agents on disinfection treatment has largely been ignored. In this study, we find that dormant amoeba spores, a frequently found protist in drinking water systems, can protect their intracellular bacteria from drinking water disinfection. Bacteria-containing amoeba spores were constructed and treated with various disinfection techniques (Cl2, ClO2, and UV254). The three disinfection methods could kill the bacteria alone efficiently (6-log inactivation). However, the inactivation efficiency of bacteria that hid within amoeba spore was significantly inhibited (2-3-log inactivation). We also found that inactivated amoeba spores can still protect their intracellular bacteria. This study provides direct evidence that viable and inactivated amoeba spores can protect their hitchhiking bacteria from disinfection treatment, which is crucial for future decision-making about the dosage for sufficient bacterial disinfection in drinking water systems.

Kinetics and Mechanisms of Virus Inactivation by Chlorine Dioxide in Water Treatment: A Review.

Chlorine dioxide (ClO2), an alternative disinfectant to chlorine, has been widely applied in water and wastewater disinfection. This paper aims at presenting an overview of the inactivation kinetics and mechanisms of ClO2 with viruses. The inactivation efficiencies vary greatly among different virus species. The inactivation rates for different serotypes within a family of viruses can differ by over 284%. Generally, to achieve a 4-log removal, the exposure doses, also being referred to as Ct values (mutiplying the concentration of ClO2 and contact time) vary in the range of 0.06-10 mg L-1 min. Inactivation kinetics of viruses show two phases: an initial rapid inactivation phase followed by a tailing phase. Inactivation rates of viruses increase as pH or temperature increases, but show different trends with increasing concentrations of dissolved organic matter (DOM). Both damages in viral proteins and in the 5' noncoding region within the genome contribute to virus inactivation upon ClO2 disinfection.

Exploration of reaction rates of chlorine dioxide with tryptophan residue in oligopeptides and proteins.

Chlorine dioxide (ClO2), an alternative disinfectant to chlorine, has a superior ability to inactivate microorganisms, in which protein damage has been considered as the main inactivation mechanism. However, the reactivity of ClO2 with amino acid residues in oligopeptides and proteins remains poorly investigated. In this research, we studied the reaction rate constants of ClO2 with tryptophan residues in five heptapeptides and four proteins using stopped-flow or competition kinetic method. Each heptapeptide and protein contain only one tryptophan residue and the reactivity of tryptophan residue with ClO2 was lower than that of free tryptophan (3.88 × 104 (mol/L)-1sec-1 at pH 7.0). The neighboring amino acid residues affected the reaction rates through promoting inter-peptide aggregation, changing electron density, shifting pKa values or inducing electron transfer via redox reactions. A single amino acid residue difference in oligopeptides can make the reaction rate constants differ by over 60% (e.g. 3.01 × 104 (mol/L)-1sec-1 for DDDWNDD and 1.85 × 104 (mol/L)-1sec-1 for DDDWDDD at pH 7.0 (D: aspartic acid, W: tryptophan, N: asparagine)). The reaction rates of tryptophan-containing oligopeptides were also highly pH-dependent with higher reactivity for deprotonated tryptophan than the neutral specie. Tryptophan residues in proteins spanned a 4-fold range reactivity toward ClO2 (i.e. 0.84 × 104 (mol/L)-1sec-1 for ribonuclease T1 and 3.21 × 104 (mol/L)-1sec-1 for melittin at pH 7.0) with accessibility to the oxidant as the determinating factor. The local environment surrounding the tryptophan residue in proteins can also accelerate the reaction rates by increasing the electron density of the indole ring of tryptophan or inhibit the reaction rates by inducing electron transfer reactions. The results are of significance in advancing understanding of ClO2 oxidative reactions with proteins and microbial inactivation mechanisms.

Chlorite formation during ClO2 oxidation of model compounds having various functional groups and humic substances.

Chlorine dioxide (ClO2) has been used as an alternative to chlorine in water purification to reduce the formation of halogenated by-products and give superior inactivation of microorganisms. However, the formation of chlorite (ClO2-) is a major consideration in the application of ClO2. In order to improve understanding in ClO2- formation kinetics and mechanisms, this study investigated the reactions of ClO2 with 30 model compounds, 10 humic substances and 2 surface waters. ClO2- yields were found to be dependent on the distribution of functional groups. ClO2 oxidation of amines, di- and tri-hydroxybenzenes at pH 7.0 had ClO2- yields >50%, while oxidation of olefins, thiols and benzoquinones had ClO2- yields <50%. ClO2- yields from humic substances depended on the ClO2 dose, pH and varied with different reaction intervals, which mirrored the behavior of the model compounds. Phenolic moieties served as dominant fast-reacting precursors (during the first 5 min of disinfection). Aromatic precursors (e.g., non-phenolic lignins or benzoquinones) contributed to ClO2- formation over longer reaction time (up to 24  h). The total antioxidant capacity (indication of the amount of electron-donating moieties) determined by the Folin-Ciocalteu method was a good indicator of ClO2-reactive precursors in waters, which correlated with the ClO2 demand of waters. Waters bearing high total antioxidant capacity tended to generate more ClO2- at equivalent ClO2 exposure, but the prediction in natural water should be conservative.

ClO2 pre-oxidation changes the yields and formation pathways of chloroform and chloral hydrate from phenolic precursors during chlorination.

Phenolic moieties in natural organic matter (NOM) are important precursors of disinfection by-products (DBPs). In this study, the formation of chloral hydrate from chlorination of seventeen phenolic compounds, including mono-, di- and tri-hydroxybenzenes, were evaluated and the role of chlorine dioxide (ClO2) pre-oxidation on its formation pathways was explored. Chloroform, was also evaluated for comparison. Chlorination of resorcinol exhibited the highest chloral hydrate yield (2.83 ±â€¯0.13%) followed by chlorination of 2,4,6-trichlorophenol (0.61 ±â€¯0.03%). The median of chloral hydrate yields from the tested phenolic compounds was 0.22%. ClO2 pre-oxidation reduced the yields of chloroform from phenol derivatives by 37-97%, except 4-methoxyphenol, catechol and 2,3-dihydroxyphenol. On the contrary, ClO2 pre-oxidation of di- and tri-hydroxybenzenes tended to increase chloral hydrate yields in post-chlorination. Mixed results (both increases and decreases) were observed in chloral hydrate formation from chlorination of mono-hydroxybenzenes after ClO2 pre-oxidation. The changes of their formation were dependent on ClO2 pre-oxidation time and dosages. Identification of transformation products suggested that phenolic compounds were mainly converted to unsaturated carbonyl structures by ClO2. Chlorine substituted benzoquinones and cyclopent-4-ene-1,3-diones were important transformation products after a series of ring open, decarboxylation, hydrolysis and chlorine substitution reactions. The changes in the formation yields of chloral hydrate and chloroform were governed by the difference in initial phenolic precursors and the transformation products after ClO2 pre-oxidation. ClO2 pre-oxidation in water treatment can effectively reduce chloroform formation but may have a risk of increasing chloral hydrate formation.