Ozone Decay Research Articles

Mathematical modeling of ozone decomposition processes in wastewater treatment: A lumped kinetic approach with initial ozone demand

Ozone-based processes involve complex reaction networks and exhibit matrix-dependent decomposition patterns when dosed to wastewater effluents. Existing models for ozone decomposition are either too complex or not sufficiently descriptive of the regime manifested during initial ozone demand and decay. Models incorporating detailed reactions have shown limited applicability due to the high number of initial states and state variables involved. This study introduces a new mathematical model that balances accuracy and complexity in describing the main phases of ozone decomposition in secondary wastewater effluents. Specifically, a simplified model is proposed based on lumped variables, including initial ozone demand, two classes of organic matter (slow and fast reacting), radical forming (and ozone-decomposing) compounds, radical scavengers, and a hypothetical target contaminant. Results revealed that the model can predict with reasonable accuracy both the rapid initial ozone demand (occurring at very short timescales <10 s) and the slower ozone decomposition processes (occurring at longer timescales >30 s). A global sensitivity analysis was also conducted to further model refinement and simplification, which led to the elimination of three reactions connected to the generation and consumption of radicals (threshold |RXY| ≥ 0.05). Satisfactorily low residual values (RMSE≤7·10−6 M) were observed in all cases. Finally, the adequacy of the model was further tested against an independent set of ozone decomposition experiments obtained from the literature, confirming its suitability in describing ozone decomposition in secondary wastewater effluents with initial ozone demand.

Prediction of hydroxyl radical exposure during ozonation using different machine learning methods with ozone decay kinetic parameters

The abatement of micropollutants by ozonation can be accurately calculated by measuring the exposures of molecular ozone (O3) and hydroxyl radical (•OH) (i.e., ∫[O3]dt and ∫[•OH]dt). In the actual ozonation process, ∫[O3]dt values can be calculated by monitoring the O3 decay during the process. However, calculating ∫[•OH]dt is challenging in the field, which necessitates developing models to predict ∫[•OH]dt from measurable parameters. This study demonstrates the development of machine learning models to predict ∫[•OH]dt (the output variable) from five basic input variables (pH, dissolved organic carbon concentration, alkalinity, temperature, and O3 dose) and two optional ones (∫[O3]dt and instantaneous ozone demand, IOD). To develop the models, four different machine learning methods (random forest, support vector regression, artificial neural network, and Gaussian process regression) were employed using the input and output variables measured (or determined) in 130 different natural water samples. The results indicated that incorporating ∫[O3]dt as an input variable significantly improved the accuracy of prediction models, increasing overall R2 by 0.01−0.09, depending on the machine learning method. This suggests that ∫[O3]dt plays a crucial role as a key variable reflecting the •OH-yielding characteristics of dissolved organic matter. Conversely, IOD had a minimal impact on the accuracy of the prediction models. Generally, machine-learning-based prediction models outperformed those based on the response surface methodology developed as a control. Notably, models utilizing the Gaussian process regression algorithm demonstrated the highest coefficients of determination (overall R2 = 0.91−0.95) among the prediction models.

Tailored Metal-Organic Frameworks for Water Purification: Perfluorinated Fe-MOFs for Enhanced Heterogeneous Catalytic Ozonation.

An industrially viable catalyst for heterogeneous catalytic ozonation (HCO) in water purification requires the characteristics of good dispersion of active species on its surface, efficient electron transfer for ozone decay, and maximum active species utilization. While metal-organic frameworks (MOFs) represent an attractive platform for HCO, the metal nodes in the unmodified MOFs exhibit low catalytic activity. Herein, we present a perfluorinated Fe-MOF catalyst by substituting H atoms on the metalated ligands with F atoms (termed 4F-MIL-88B) to induce structure evolution. The Lewis acidity of 4F-MIL-88B was enhanced via the formation of Fe nodes, tailoring the electron distribution on the catalyst surface. As a result of catalyst modification, the rate constant for degradation of the target compounds examined increased by ∼700% compared with that observed for the unmodified catalyst. Experimental evidence and theoretical calculations showed that the modulated polarity and the enhanced electron transfer between the catalyst and ozone molecules contributed to the adsorption and transformation of O3 to •OH on the catalyst surface. Overall, the results of this study highlight the significance of tailoring the metalated ligands to develop highly efficient and stable MOF catalysts for HCO and provide an in-depth mechanistic understanding of their structure-function evolution, which is expected to facilitate the applications of nanomaterial-based processes in water purification.

Virus inactivation in low ozone exposure water reuse applications

In drinking water applications, an ozone exposure (Ct) based framework has been historically used to validate ozone disinfection. However, significant viral inactivation can be achieved with little to no measurable ozone exposure. Additionally, ozone exposure depends on multiple water quality variables as well as the calculation/ozone measurement method used. In this study, we evaluated alternative ozone monitoring frameworks as well as the impact of water quality variables on ozone decay kinetics and virus/coliform inactivation. Here we show that both change in UV254 absorbance and applied O3:TOC were well correlated with viral inactivation and these frameworks were resilient to changes in water quality. Both increasing temperature (12–30 ⁰C) and pH (5.5–8.4) was shown to significantly increase the ozone decay rate and decreased the resulting ozone exposure by as much as ∼90% in the case of pH. However, due to the increased reaction rate of ozone with viruses at elevated temperature and pH, there was only a minor impact (∼20% in the case of pH) in overall disinfection performance for a given O3:TOC. These frameworks were also considered for variable source water with TOC (5–11 mg/L) and TSS (1.2–5.8 mg/L). Change in UV254 absorbance or applied ozone dose (mg/L) were the strongest indicators of disinfection performance for source waters of variable TOC, however site-specific testing may be needed to apply this framework. Challenge testing with influent nitrite indicated that ozone disinfection performance is significantly impacted (>50% reduction in inactivation) in the presence of nitrite thus enforcing the importance of accounting for this value in the applied ozone dose. Multi-point ozone dissolution was investigated as an alternative ozone application method that may present a benefit with respect to overall disinfection performance especially if nitrite was present. Developing and validating these alternative monitoring frameworks and ozone application methods is imperative in water reuse applications where unnecessary elevated ozone exposure may lead to harmful byproduct formation.

Modeling of tubular membrane contactors for ozonation of water reveals reduced bromate formation with static mixers

Bromate formation and insufficient micropollutant degradation are two major problems in wastewater ozonation. The conventional process using bubble columns has the drawback of an inhomogeneous ozone distribution, causing increased bromate formation. Membrane contactors are a promising alternative as they can dissolve ozone bubble-free. This work presents a simulation of a tubular membrane contactor in COMSOL Multiphysics that includes flow, mass transfer, ozone decay, and reactions of organic molecules and bromide with ozone and hydroxyl radicals. Gaseous ozone and water flow on the lumen and shell side of the membrane, respectively. Static mixers are placed in the water channel, coaxial between the membrane and housing. The simulations show a 75% increase in ozone flux through the membrane, a homogenized ozone distribution, and 13 times higher degradation of a medium-oxidizable micropollutant in the presence of additional static mixers. Furthermore, static mixers enable the use of a lower gaseous ozone concentration, resulting in 31% lower bromate formation at the same ozone exposure without affecting micropollutant degradation. Overall, we demonstrate that membrane contactors with static mixers can be used as a strategy to reduce bromate formation.

Is catalytic ozonation always an efficient treatment for refractory pollutant in various water matrices?

In this study, surrogate indicators (·OH yield and Rct value) were developed to identify whether homogeneous and heterogeneous catalysts should be added during ozonation of refractory pollutants. The abatement of atrazine (ATZ) was in the order of O3/H2O2 process (94 %) > O3/γ-Al2O3 process (70 %) > ozonation alone process (55 %) in synthetic water samples at pH 7, which was in agreement with the order of ·OH yield and Rct value. However, the abatement of ATZ during ozonation alone process (0.64–0.62) was higher than O3/H2O2 process (0.63–0.60) and O3/γ-Al2O3 process (0.48–0.49) in the presence of high dosage of humic acid (HA, 3.38 × 10−1–4.50 × 10−1 mg C/L) at pH 7. The abatement of ATZ was linearly proportional to ·OH yield, whereas it was not linearly proportional to Rct value in the synthetic water samples containing HA at pH7. The abatement of ATZ during ozonation alone process was higher than that during catalytic ozonation process by one-time ozone dosing method in real water. The abatement of ATZ during O3/H2O2 process and O3/γ-Al2O3 process were higher than that during ozonation alone process by three-time ozone dosing method in real water, which was linearly proportional to ·OH yield and Rct value. The residual DOM in phase III become recalcitrant to ozone, which could be decomposed by catalyst forming ·OH. Overall, this result implies that the comparison of ·OH yield and Rct value between ozone decay by DOM in various water matrices and by catalyst should be concerned before the addition of catalyst during ozonation process was applied in real water.

KINETIC EQUATIONS FOR RADICAL-CHAIN OXIDATION INVOLVING PROCESS-INHIBITING ALKYL (OR HYDRO)TETRAOXYL FREE RADICAL

The derivation of kinetic equations for the oxidation processes by the free-radical nonbranched-chain mechanism is shown. This derivation is based on the proposed reaction scheme for the initiated addition of free radicals to the multiple bond of the molecular oxygen includes the addition reaction of the peroxyl free radical to the oxygen molecule to form the tetraoxyl free radical. This reaction competes with chain propagation reactions through a reactive free radical. The chain evolution stage in this scheme involves a few of free radicals, one of which – alkyl(or hydro)tetraoxyl – is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. The rate equations (containing one to three parameters to be determined directly) are deduced using the quasi-steady-state treatment. These kinetic equations were used to describe the γ-induced nonbranched-chain processes of free-radical oxidation of liquid o-xylene at 373 K and hydrogen dissolved in water containing various amounts of oxygen at 296 K. The ratios of rate constants of competing reactions and rate constants of addition reactions to the molecular oxygen are defined. In these processes the oxygen with the increase of its concentration begins to act as an oxidation autoinhibitor (or an antioxidant), and the rate of peroxide formation as a function of the dissolved oxygen concentration has a maximum. It is shown that a maximum in these curves arises from the competition between hydrocarbon (or hydrogen) molecules and dioxygen for reacting with the emerging peroxyl 1:1 adduct radical. From the energetic standpoint possible nonchain pathways of the free-radical oxidation of hydrogen and the routes of ozone decay via the reaction with the hydroxyl free radical in the upper atmosphere (including the addition yielding the hydrotetraoxyl free radical, which can be an intermediate in the sequence of conversions of biologically hazardous UV radiation energy) were examined. The energetics of the key radical-molecule gas-phase reactions is considered.

Treatability of 18 taste and odor compounds in drinking water using oxidation

AbstractThe occurrence of taste and odor (T&amp;O) compounds in drinking water can lead to public concern about quality when left unaddressed, therefore suitable treatment is needed. This study evaluated the treatability of 18 T&amp;O compounds using chlorine, permanganate, and ozone in MilliQ and river water. Nine T&amp;O compounds showed complete oxidation (&gt;99% removal) in all water matrices by ozone. Most of the remaining T&amp;O compounds were removed to &gt;50% by ozone. Alkalinity, pH, and natural organic matter (NOM) had a significant impact on the decay of ozone. Chlorine and permanganate were ineffective (removal &lt;30%) for 2‐methylisoborneol (2‐MIB), geosmin, hexanal, pyrazines, and haloanisoles. Although chlorine achieved complete removal for alkyl sulfides and indole, it was only partially effective for aldehydes and ketones. Permanganate was more effective than chlorine in oxidizing unsaturated aldehydes and ketones. Increased NOM and pH reduced oxidation effectiveness for chlorine, but not permanganate.

Effective and mechanistic insights into reverse osmosis concentrate of landfill leachate treatment using coagulation-catalytic ozonation-bioaugmentation-based AnMBR

Landfill leachate membrane concentrates containing high concentrations of organics pose a major threat to the environment, and efficient treatment methods are urgent issue. In this study, a coagulation-catalytic ozonation-bioaugmentation-based anaerobic membrane bioreactor (CCOB-AnMBR) process was applied to treat reverse osmosis concentrate (ROC) of landfill leachate. Compared with polyaluminum ferric chloride (PAFC) and prefrontal cortex (PFC), coagulation using polyferric sulfate (PFS) effectively removed refractory contaminants including macro molecular organics (MMOs), benzene ring compounds (BRCs), humic acid (HA), and fulvic acid (FvA) in ROC of landfill leachate, with average 78.3%, 53.5%, 34.7% and 34.3%, respectively. Catalytic ozonation with MnOx-CeOx-Al2O3 increased the biodegradability index by degrading refractory organic compounds, which facilitated subsequent biological treatment of ROC. The oxidation of mostly occurs at the solid–liquid interface and the presence of MnOx-CeOx-Al2O3 nanocatalyst enhanced ozone decay and increased generation of hydroxyl radical (•OH) and singlet oxygen (1O2) in ROC. In addition, bioaugmentation using recombinant genetically engineered Desulfovibrio vulgaris expressing Sat and dsrAB (rGEDEV-sds) promoted metabolism of sulfate by driving transfer sulfate from the environment into the cell and sulfate dissimilation reduction process. Bioaugmentation-based AnMBR (Bio-AnMBR) caused complete degradation of the total organic carbon (TOC), enhanced degradation of leachate pollutions, and decreased the concentration of sulfate in ROC. The macro molecular organics, refractory organic contaminants, the residual coagulation-resistant substances (CRS), and heavy metal were effectively degraded in the Bio-AnMBR system. Furthermore, CCOB-AnMBR exhibits high processing efficiency in the degradation of the contaminants in ROC of landfill leachate. Overall, this excellent performance proves the feasibility and elucidates the mechanism of CCOB-AnMBR process for the removal of contaminants in ROC of landfill leachate.

The Role of Reactive Oxygen Species in Plant Response to Radiation.

Radiation is widespread in nature, including ultraviolet radiation from the sun, cosmic radiation and radiation emitted by natural radionuclides. Over the years, the increasing industrialization of human beings has brought about more radiation, such as enhanced UV-B radiation due to ground ozone decay, and the emission and contamination of nuclear waste due to the increasing nuclear power plants and radioactive material industry. With additional radiation reaching plants, both negative effects including damage to cell membranes, reduction of photosynthetic rate and premature aging and benefits such as growth promotion and stress resistance enhancement have been observed. ROS (Reactive oxygen species) are reactive oxidants in plant cells, including hydrogen peroxide (H2O2), superoxide anions (O2•-) and hydroxide anion radicals (·OH), which may stimulate the antioxidant system of plants and act as signaling molecules to regulate downstream reactions. A number of studies have observed the change of ROS in plant cells under radiation, and new technology such as RNA-seq has molecularly revealed the regulation of radiative biological effects by ROS. This review summarized recent progress on the role of ROS in plant response to radiations including UV, ion beam and plasma, and may help to reveal the mechanisms of plant responses to radiation.

Effects of vegetables and fruit with varying physical damage, fungal infection, and soil contamination on stability of aqueous ozone

The application of aqueous solutions of ozone for surface disinfection is an effective novel green technology with a potential for replacing the use of persistent chemicals in postharvest treatments. However, successful disinfection requires certain levels of ozone to be maintained throughout the process. The decay rates of aqueous ozone were found to vary with the presence of different fruit and vegetables commodities (apples, carrots, onions, celeriac, and pears). Pure aqueous ozone had a half-life of 3200 s, whereas the half-life of ozone was found to range with increasing cross-cut areas between 2177 and 291 s for apples, 573 and 345 s for carrots, 541 and 113 s for onions, 2800 and 253 s for pears, and 362 and 165 s for celeriac. With soil particles present, the ozone half-life dropped to 59 s for celeriac. Parallel measurements reported strong to moderate effect of soil particles (51–626 s, 10 g soil/L ozonated water), and naturally occurring fungi (850–2294 s, 0.25 g fungi mix/L ozonated water) on ozone half-life. In summary, presence of organic compounds, notably by damaged commodities, increase ozone decay and illustrate the need to correctly identify important ozone-depleting parameters, which is crucial for understanding the efficiency of ozone-based washing systems.

폐수방류수 오존처리시 오존 및 OH 라디칼 노출량 기반 미량유기오염물질 제거 예측

Municipal wastewater is a major source of contaminants of emerging concern in aquatic environments. Many studies have proven the effectiveness of ozonation for the removal of micropollutants, though the composition of the wastewater matrix influences the oxidation potential during this process. The ozone decomposition rate consists of two stages: instantaneous ozone consumption and slower ozone decay. In particular, with instantaneous ozone consumption, 62.8-79.7% of the initial ozone injection concentration is consumed. Determining the appropriate ozone dosage for wastewater ozonation is complicated by the complexity of the wastewater matrix composition. The purpose of this study was to propose a chemical kinetic model for the prediction of micropollutant removal during the ozonation of wastewater effluent. A kinetics approach based on the measurement of ozone and hydroxyl radical(·OH) exposure was proposed to predict the micropollutant removal efficiency. In this study, a batch-type ozone reactor was set up to measure the ozone and OH radical exposure during wastewater ozonation. Ozone and OH radical exposure was proportional to the initial dose of ozone, while OH radical exposure was found to be proportional to ozone exposure, though the deviation was relatively high at 1.0 to 1.5 gO³/gDOC. The calculated OH radical exposure was 3.0×10^-10 to 5.3×10^-10M·s. Of the target micropollutants, acetaminophen, sulphamethoxazole, andnaproxen, which are highly reactive with ozone and OH radicals, exhibited a removal rate of more than 80% at an ozone injection rate of 0.75 gO³/gDOC.

Kinetics and mechanism of ozonation to treat Microcystis-laden source waters affected by cell-viability

Toxic cyanobacteria are challenging drinking water safety globally, and their cell-viability declines at decay stage of a succussive bloom. Ozone might be a more effective oxidant to treat both high- and low-viability cyanobacteria than other common oxidants (e.g., chlorine, potassium permanganate). However, previous studies only conducted ozonation experiments using high-viability cyanobacteria, and potential influences of cell-viability on ozonation process, remains unknown. In this study, kinetics of ozone decay, cell inactivation, membrane destruction, and cyanotoxin fate of high- and low-viability Microcystis (the most common genus), was investigated, and associated mechanism was discussed. Results showed that low-viability Microcystis exhibited a higher rate constant of membrane destruction (665–744 M−1 s−1) than high-viability Microcystis (364–600 M−1 s−1) by equal concentrations of ozone, ascribed to loosely gelatinous sheath comprised with fewer organic matters as oxidant scavengers. Meanwhile, a higher rate constant of photosynthetic inactivation induced by ozonation, was observed for low-viability Microcystis (312–364 M−1 s−1) than that for high-viability Microcystis (168–294 M−1 s−1). However, elevated aromatic organics competitively inhibited microcystin ozonation for low-viability Microcystis, and hydroxyl radicals for microcystin oxidation could be reduced by elevated organic loads and alkalinity. Moreover, elevated ozone exposure (>51 mg min L−1) did not totally oxidize microcystin with a residual of 30 μg L−1 for low-viability Microcystis. These findings suggested that elevated microcystin risk would be the great barrier to limit ozonation application for low-viability Microcystis, even with benefits of higher cell inactivation compared to high-viability Microcystis.

Ozone as an alternative fumigant for controlling Callosobruchus maculatus (F.) (Coleoptera: Chrysomelidae) in cowpea beans

This study aimed to characterize the reaction kinetics of ozone gas in cowpea beans, to determine its insecticidal activity against Callosobruchus maculatus adult insects, and to assess grain quality after ozonation. Samples of 3.0 kg of cowpea beans were exposed to ozone gas at inlet concentrations of 500, 1,500, 2,500, and 3500 μg L−1, at a specific flow rate of 0.5 L min−1 kg−1 of grains. Moisture content, cooking time, germination percentage, and electric conductivity of the grains were analyzed. Grain quality was evaluated after exposure to the gas for periods corresponding to the lethal time to 95% of the insects (LT95), at each ozone concentration. The cowpea samples exposed to ozone at the inlet concentrations of 500, 1,500, 2,500, and 3500 μg L−1 got saturated with the gas after 45.18, 20.11, 16.86, and 14.70 min, respectively. The first-order kinetic model provided the best fit to the ozone decay data in cowpea beans. The average half-life of ozone in the grains was 6.88 ± 0.48 min. The estimated lethal times at the inlet ozone concentrations of 500, 1,500, 2,500, and 3500 μg L−1 were 777.27, 133.27, 84.29, and 52.33 min (LT50), and 1698.00, 331.20, 157.07, and 84.40 min (LT95), respectively. Callosobruchus maculatus adult progeny declined as the exposure time increased, at all inlet ozone concentrations. Cowpea bean quality did not change after ozone exposure, except for the electric conductivity, which differed between the grains exposed to ozone and those to atmospheric air. The results of this study indicate that ozone gas controls C. maculatus effectively and, in general, does not change the quality of cowpea beans at the inlet concentrations and exposure times appraised.

Analysis of Ozonation Processes Using Coupled Modeling of Fluid Dynamics, Mass Transfer, and Chemical Reaction Kinetics.

The efficacy of oxidation of recalcitrant organic contaminants in municipal and industrial wastewaters by ozonation is influenced by chemical reaction kinetics and hydrodynamics within a reactor. A 3D computational fluid dynamics (CFD) model incorporating both multiphase flow and reaction kinetics describing ozone decay, hydroxyl radical (•OH) generation, and organic oxidation was developed to simulate the performance of continuous flow ozonation reactors. Formate was selected as the target organic in this study due to its well-understood oxidation pathway. Simulation results revealed that the dissolved ozone concentration in the reactor is controlled by rates of O3(g) interphase transfer and ozone self-decay. Simulations of the effect of various operating conditions showed that the reaction stoichiometric constraints between formate and ozone were reached; however, complete utilization of gas phase ozone was hard to achieve due to the low ozone interphase mass transfer rate. Increasing the O3(g) concentration leads to an increase in the formate removal rate by ∼5% due to an enhancement in the rate of O3(g) interphase mass transfer. The CFD model adequately describes the mass transfer occurring in the two-phase flow system and confirms that O3(g) interphase mass transfer is the rate-limiting step in contaminant degradation. The model can be used to optimize the ozone reactor design for improved contaminant degradation and ozonation efficiency.

Quantitative evaluation of the inactivation effect of ozonated water on SARS-CoV-2 based on corrected CT values

ABSTRACT There are many issues in the evaluation protocols based on CT (mg min/L) values, which have been used to assess the germicidal effect of highly oxidative and unstable ozonated water. The major problems include the carryover of culture medium components in virus inactivation assays and the reaction volume ratio between the virus suspension and ozonated water. Furthermore, it is essential to correct the CT value with the decay curve of dissolved ozone under the same conditions as the inactivation assay. In this study, these concerns were reexamined to obtain quantitative CT values. Severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) inactivation test using ozonated water prepared from pure water was assessed by determining the corrected concentration time (CCT) values. Moreover, a possible inactivation mechanism of SARS-CoV-2 was discussed with the aid of findings from this study and previous reports. The findings revealed that the CCT value required for 99.95% inactivation of SARS-CoV-2 with ozonated water was 0.97 mg·min/L. To quantitatively evaluate the SARS-CoV-2 inactivation test, the virus purification procedure during the pretreatment and the CT value correction using a dissolved ozone decay curve obtained under the same condition as the inactivation test were demonstrated to be essential. We proposed a possible mechanism of SARS-CoV-2 inactivation with ozonated water. Amino acids such as tyrosine, tryptophan, methionine, cysteine, and histidine in the SARS-CoV-2 spike protein are susceptible to oxidative attack by the ozone dissolved in water. This attack may induce structural destruction of the spike protein and inhibit its binding to the angiotensin converting enzyme 2 (ACE2) receptor, an essential host receptor for viral infection, resulting in viral inactivation and contributing to infection suppression.

"Derivation of Kinetic Equations for Free-Radical Nonbranched-Chain Processes of Hydrocarbon and Hydrogen Oxidation"

The derivation of kinetic equations for the oxidation processes by the free-radical nonbranched-chain mechanism is shown. This derivation is based on the proposed reaction scheme for the initiated addition of free radicals to the multiple bond of the molecular oxygen includes the addition reaction of the peroxyl free radical to the oxygen molecule to form the tetraoxyl free radical. This reaction competes with chain propagation reactions through a reactive free radical. The chain evolution stage in this scheme involves a few of free radicals, one of which (tetraoxyl) is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. The rate equations (containing one to three parameters to be determined directly) are deduced using the quasi-steady-state treatment. The kinetic description with use the obtained rate equations is applied to the γ-induced nonbranched-chain processes of the free-radical oxidation of liquid o-xylene at 373 K and hydrogen dissolved in water containing different amounts of dioxygen at 296 K. The ratios of rate constants of competing reactions and rate constants of addition reactions to the molecular oxygen are defined. In these processes the oxygen with the increase of its concentration begins to act as an oxidation autoinhibitor (or an antioxidant), and the rate of peroxide formation as a function of the dissolved oxygen concentration has a maximum. It is shown that a maximum in these curves arises from the competition between hydrocarbon (or hydrogen) molecules and dioxygen for reacting with the emerging peroxyl 1:1 adduct radical. From the energetic standpoint possible nonchain pathways of the free-radical oxidation of hydrogen and the routes of ozone decay via the reaction with the hydroxyl free radical in the upper atmosphere (including the addition yielding the hydrotetraoxyl free radical, which can be an intermediate in the sequence of conversions of biologically hazardous UV radiation energy) were examined. The energetics of the key radical-molecule gas-phase reactions is considered.

Ozone Consumption by Soils: A Critical Factor in In Situ Ozonation Processes

In situ chemical ozonation (ISCO3), in which gaseous ozone is being injected into the subsurface, is a common method for remediating contaminated groundwater that is largely affected by the inevitable consumption of ozone by soil itself (rather than the target contaminants). In this study, ozone consumption by two main soil types of Israeli coastline aquifer was examined. Iron-rich soil showed considerably higher reactivity than did calcareous soil. We further investigated the effect of both physical and chemical soil characteristics on finite and catalytic ozone decay, hydroxyl-radical formation, and ozone transport behavior. Ozone consumption increased by >90% in the presence of fine soil particles (<100 μm), resulting from the large number of reactive sites and the higher content of ozone consumers compared to coarse soil particles. Soil organic matter consumed ozone twice as fast as iron components, promoted radical formation at higher rates, and mainly acted as a finite ozone consumer. In continuously fed column experiments, the reactions with iron components dominate catalytic ozone consumption during transport in porous media. Overall, this study demonstrates that the characterization of ozone reactions in soil can be helpful in evaluating the feasibility and efficiency of ISCO3 and inform the design of ISCO3 treatment, e.g., the need to inject additional radical promoters.

Development of an Experimental Setup for Real-Time In-Line Dissolved Ozone Measurement for Medical Therapy

ABSTRACT Ozone therapy is established in clinical applications since many decades, such as treatment of infections or herniated discs. However, in-line monitoring of ozone concentrations is challenging and therefore not performed by default. We developed an experimental setup to measure the in-line ozone concentration in water in real-time with a spectroscopic sensor. Thereby, the experimental setup enables the calibration and evaluation of newly evolved ozone sensors. The results for ozone concentration measurement with the spectroscopic sensor and the colorimetric photometer show a very good correlation. Furthermore, the ozone decay curves measured with our experimental setup highly correlate with those of previous research.

Modelling ozone disinfection process for creating COVID-19 secure spaces

PurposeA novel modelling approach is proposed to study ozone distribution and destruction in indoor spaces. The level of ozone gas concentration in the air, confined within an indoor space during an ozone-based disinfection process, is analysed. The purpose of this work is to investigate how ozone is distributed in time within an enclosed space.Design/methodology/approachA computational methodology for predicting the space- and time-dependent ozone concentration within the room across the consecutive steps of the disinfection process (generation, dwelling and destruction modes) is proposed. The emission and removal of ozone from the air volume are possible by means of a generator located in the middle of the room. This model also accounts for ozone reactions and decay kinetics, and gravity effect on the air.FindingThis work is validated against experimental measurements at different locations in the room during the disinfection cycle. The numerical results are in good agreement with the experimental data. This comparison proves that the presented methodology is able to provide accurate predictions of the time evolution of ozone concentration at different locations of the enclosed space.Originality/valueThis study introduces a novel computational methodology describing solute transport by turbulent flow for predicting the level of ozone concentration within a closed room during a COVID-19 disinfection process. A parametric study is carried out to evaluate the impact of system settings on the time variation of ozone concentration within the space considered.