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Post-etching method using dilute acid solutions is an effective technology to modulate the surface compositions of metal-oxide catalysts. Here the α-MnO2 catalyst treated with 0.1 mol/L nitric acid exhibits higher ozone decomposition activity at high relative humidity than the counterpart treated with acetic acid. Besides the increases in surface area and lattice dislocation, the improved activity can be due to relatively higher Mn valence on the surface and newly-formed Brønsted acid sites adjacent to oxygen vacancies. The remnant nitro species deposited on the catalyst by nitric acid treatment is ideal hydrophobic groups at ambient conditions. The decomposition route is also proposed based on the DRIFTS and DFT calculations: ozone is facile to adsorb on the oxygen vacancy, and the protonic H of Brønsted acid sites bonds to the terminal oxygen of ozone to accelerate its cleavage to O2, reducing the reaction energy barrier of O2 desorption.
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Umidade , Compostos de Manganês , Óxidos , Ozônio , Ozônio/química , Óxidos/química , Compostos de Manganês/química , Catálise , Modelos QuímicosRESUMO
A novel system for measuring net photochemical ozone production rates in the atmosphere based on cavity ring-down spectroscopy (OPR-CRDS) was developed. The system consists of two chambers (a reaction chamber and a reference chamber) and a dual-channel Ox-CRDS detector. To minimize the wall loss of Ox in the chambers, the inner surfaces of both chambers are coated with Teflon film. The performance of the OPR-CRDS system was characterized. It was found that even though the photolysis frequency (J value) decreased by 10%, the decrease in the P(O3) caused by the ultraviolet-blocking film coating was less than 3%. The two chambers had a good consistency in the mean residence time and the measurement of NO2 and Ox under the condition of no sunlight. The detection limit of the OPR-CRDS was determined to be 0.20 ppbv/hr. To further verify the accuracy of the system, the direct measurement values of the OPR-CRDS system were compared with the calculation results based on radical (OH, HO2, and RO2) reactions, and a good correlation was obtained between the measured and calculated values. Finally, the developed instrument was applied to obtain the comprehensive field observations at an urban site in the Yangtze River Delta (China) for 40 days, the time series and change characteristics of the P(O3) were obtained directly, and the good environmental adaptability and stability of the OPR-CRDS system were demonstrated. It is expected that the new instrument will be beneficial to investigations of the relationship between P(O3) and its precursors.
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Poluentes Atmosféricos , Monitoramento Ambiental , Ozônio , Ozônio/análise , Monitoramento Ambiental/métodos , Monitoramento Ambiental/instrumentação , Poluentes Atmosféricos/análise , Análise Espectral/métodos , China , Atmosfera/química , FotóliseRESUMO
VOCs (Volatile organic compounds) exert a vital role in ozone and secondary organic aerosol production, necessitating investigations into their concentration, chemical characteristics, and source apportionment for the effective implementation of measures aimed at preventing and controlling atmospheric pollution. From July to October 2020, online monitoring was conducted in the main urban area of Shijiazhuang to collect data on VOCs and analyze their concentrations and reactivity. Additionally, the PMF (positive matrix factorization) method was utilized to identify the VOCs sources. Results indicated that the TVOCs (total VOCs) concentration was (96.7 ± 63.4 µg/m3), with alkanes exhibiting the highest concentration of (36.1 ± 26.4 µg/m3), followed by OVOCs (16.4 ± 14.4 µg/m3). The key active components were alkenes and aromatics, among which xylene, propylene, toluene, propionaldehyde, acetaldehyde, ethylene, and styrene played crucial roles as reactive species. The sources derived from PMF analysis encompassed vehicle emissions, solvent and coating sources, combustion sources, industrial emissions sources, as well as plant sources, the contribution of which were 37.80%, 27.93%, 16.57%, 15.24%, and 2.46%, respectively. Hence, reducing vehicular exhaust emissions and encouraging neighboring industries to adopt low-volatile organic solvents and coatings should be prioritized to mitigate VOCs levels.
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Poluentes Atmosféricos , Monitoramento Ambiental , Compostos Orgânicos Voláteis , Compostos Orgânicos Voláteis/análise , Poluentes Atmosféricos/análise , China , Emissões de Veículos/análise , Cidades , Poluição do Ar/estatística & dados numéricos , Poluição do Ar/prevenção & controle , Poluição do Ar/análiseRESUMO
Severe ground-level ozone (O3) pollution over major Chinese cities has become one of the most challenging problems, which have deleterious effects on human health and the sustainability of society. This study explored the spatiotemporal distribution characteristics of ground-level O3 and its precursors based on conventional pollutant and meteorological monitoring data in Zhejiang Province from 2016 to 2021. Then, a high-performance convolutional neural network (CNN) model was established by expanding the moment and the concentration variations to general factors. Finally, the response mechanism of O3 to the variation with crucial influencing factors is explored by controlling variables and interpolating target variables. The results indicated that the annual average MDA8-90th concentrations in Zhejiang Province are higher in the northern and lower in the southern. When the wind direction (WD) ranges from east to southwest and the wind speed (WS) ranges between 2 and 3 m/sec, higher O3 concentration prone to occur. At different temperatures (T), the O3 concentration showed a trend of first increasing and subsequently decreasing with increasing NO2 concentration, peaks at the NO2 concentration around 0.02 mg/m3. The sensitivity of NO2 to O3 formation is not easily affected by temperature, barometric pressure and dew point temperature. Additionally, there is a minimum [Formula: see text] at each temperature when the NO2 concentration is 0.03 mg/m3, and this minimum [Formula: see text] decreases with increasing temperature. The study explores the response mechanism of O3 with the change of driving variables, which can provide a scientific foundation and methodological support for the targeted management of O3 pollution.
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Poluentes Atmosféricos , Poluição do Ar , Cidades , Monitoramento Ambiental , Redes Neurais de Computação , Ozônio , Ozônio/análise , Poluentes Atmosféricos/análise , China , Poluição do Ar/estatística & dados numéricos , Análise Espaço-TemporalRESUMO
Objective weather classification methods have been extensively applied to identify dominant ozone-favorable synoptic weather patterns (SWPs), however, the consistency of different classification methods is rarely examined. In this study, we apply two widely-used objective methods, the self-organizing map (SOM) and K-means clustering analysis, to derive ozone-favorable SWPs at four Chinese megacities in 2015-2022. We find that the two algorithms are largely consistent in recognizing dominant ozone-favorable SWPs for four Chinese megacities. In the case of classifying six SWPs, the derived circulation fields are highly similar with a spatial correlation of 0.99 between the two methods, and the difference in the mean frequency of each SWP is less than 7%. The six dominant ozone-favorable SWPs in Guangzhou are all characterized by anomaly higher radiation and temperature, lower cloud cover, relative humidity, and wind speed, and stronger subsidence compared to climatology mean. We find that during 2015-2022, the occurrence of ozone-favorable SWPs days increases significantly at a rate of 3.2 day/year, faster than the increases in the ozone exceedance days (3.0 day/year). The interannual variability between the occurrence of ozone-favorable SWPs and ozone exceedance days are generally consistent with a temporal correlation coefficient of 0.6. In particular, the significant increase in ozone-favorable SWPs in 2022, especially the Subtropical High type which typically occurs in September, is consistent with a long-lasting ozone pollution episode in Guangzhou during September 2022. Our results thus reveal that enhanced frequency of ozone-favorable SWPs plays an important role in the observed 2015-2022 ozone increase in Guangzhou.
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Poluentes Atmosféricos , Monitoramento Ambiental , Ozônio , Tempo (Meteorologia) , Ozônio/análise , China , Poluentes Atmosféricos/análise , Poluição do Ar/estatística & dados numéricosRESUMO
Nowadays, it is still a challenge to prepared high efficiency and low cost formaldehyde (HCHO) removal catalysts in order to tackle the long-living indoor air pollution. Herein, δ-MnO2 is successfully synthesized by a facile ozonation strategy, where Mn2+ is oxidized by ozone (O3) bubble in an alkaline solution. It presents one of the best catalytic properties with a low 100% conversion temperature of 85°C for 50 ppm of HCHO under a GHSV of 48,000 mL/(g·hr). As a comparison, more than 6 times far longer oxidation time is needed if O3 is replaced by O2. Characterizations show that ozonation process generates a different intermediate of tetragonal ß-HMnO2, which would favor the quick transformation into the final product δ-MnO2, as compared with the relatively more thermodynamically stable monoclinic γ-HMnO2 in the O2 process. Finally, HCHO is found to be decomposed into CO2 via formate, dioxymethylene and carbonate species as identified by room temperature in-situ diffuse reflectance infrared fourier transform spectroscopy. All these results show great potency of this facile ozonation routine for the highly active δ-MnO2 synthesis in order to remove the HCHO contamination.
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Formaldeído , Compostos de Manganês , Óxidos , Ozônio , Ozônio/química , Compostos de Manganês/química , Formaldeído/química , Óxidos/química , Poluentes Atmosféricos/química , Oxirredução , Temperatura , Poluição do Ar em Ambientes Fechados/prevenção & controle , CatáliseRESUMO
Tropospheric ozone (TPO) is considered as a "near-term climate forcer", whose impact on climate depends on its radiative forcing (RF), which is a change in the Earth's energy flux. Here, we use the ground-based and satellite measurements during the period 2005-2020 to deduce the trends of TPO, which is significantly positive in the tropical and extra-tropical northern hemisphere (0.2-0.5 DU/yr) and southern extra-tropics (0.1-0.2 DU/yr). Furthermore, the trends derived using a multiple linear regression model (MLR) also confirm these estimates, which are about 0.05-0.1 DU/yr and the regions with higher trends (>0.06 DU/yr) are statistically significant. We also use a standalone Rapid Radiative Transfer Model coupled with a convective model (Radiative-Convective Model; RCM) to assess the climate forcing of ozone using its vertical profiles from the Modern Era Retrospective Reanalysis (MERRA)-2 reanalysis. The estimated temperature rise due to the radiative forcing of ozone in the tropical troposphere (1000-100 hPa) is about 0.2-0.3 °C for the study period. In brief, there is a positive trend in the tropospheric ozone in the tropics and extra-tropics, which is a great concern for regional warming, public health and ecosystem dynamics.
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Ultraviolet (UV) light is widely used for disinfection in indoor environments. Some wavelengths of UV light can produce high concentration of O3. UV irradiation combined with O3 may have great potential for nitration of allergens in the presence of NO2 in the air. In this study, the effects of UV irradiation on the nitration of three major indoor allergens including group â allergens of house dust mite (Der p 1 and Der f 1) and group â allergen of dog (Can f 1) in the presence of NO2 and O3 were investigated by analysis of the protein quantity, tyrosine, peptides, and nitration degree. The results showed that UV irradiation induced a significant increase in the quantity of 3-nitrotyrosine in the allergens from 0.4 ± 0.4 ng to 4.0 ± 0.8 ng. After 12 h of UV-O3 co-exposure, the total nitration degrees of the three allergens ranged from 0.1% to 0.5%, which were significantly higher than those after only O3 exposure (p < 0.05). The analysis of peptides revealed that the nitration of tyrosine was site-specific. The tyrosine Y231, which was adjacent to aspartic acid, posed the highest nitration degree of 41.1 ± 24.0% in Der p 1. The nitration degree of tyrosine Y162 was the highest (1.7 ± 0.1%) in Der f 1. Overall, this study demonstrated that UV irradiation enhanced the O3-related nitration of allergens in the air, which provides an experimental basis for the impact of daily disinfection behavior on allergens.
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Ozone (O3) pollution has become a noticeable problem in the Chengdu-Chongqing Economic Circle in China. The April-September MDA8 O3 level increases significantly by 2.26 µg m-3 year-1 from 2015 to 2023, with meteorological factors occupying merely 18 % in line with multivariate linear regression. To reveal the impact of anthropogenic emissions on O3 increase, O3 production sensitivity is accurately diagnosed by deriving localized thresholds for satellite formaldehyde (HCHO) to NO2 ratio and validated by in-situ measurements and observation-based model. Tracking volatile organic compounds (VOCs) and NOx through satellite HCHO and NO2, the O3 responses to precursor changes are assessed for long-term and special cases, and appropriate precursor reduction ratios are inferred. The results present that the transition range of satellite HCHO/NO2 from VOC-limited to NOx-limited in the region ranges from 2.7 to 4.3. The VOC-limited regime is concentrated in the urban areas of Chongqing and Chengdu as well as the central of the neighboring cities such as Deyang, Mianyang, and Meishan. The relative incremental reactivity from in-situ observations and box model at three sites in August 2019 demonstrates that O3 is most sensitive to anthropogenic VOC at urban and suburban sites, consistent with satellite results. Satellite and surface NO2 decrease at an annual rate of -2.1 % and - 2.9 % between 2015 and 2023, with larger decreases in Chengdu and Chongqing. In contrast, the trend of satellite HCHO is insignificant, indicating effective reduction in NOx but no significant reduction in VOC. This inappropriate reduction results in an increase in urban O3. The three short-term cases further validate the need for synergistic NOx and VOC reductions. Based on the relationship between O3 and satellite NO2 and HCHO, the minimum and optimal reduction ratios of VOC to NOx are 0.4:1 and 2.4:1 for the entire region, with higher ratios in Chengdu and Chongqing.
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The ozone degradation has been proven to be an effective degradation method for alginate, while the degradation mechanism remained to be unconfirmed. In this study, two high-molecular-weight alginates with different mannuronic/guluronic (G/M) ratios, HM and HG (G/M 0.49 vs 1.40), were depolymerized using established ozonation technology platform. Notably, HM can be degraded faster than HG especially within initial 30 min, indicating that the ß-1, 4-mannuronic bonds are more susceptible to be ozonated than α-1, 4-guluronic bonds. However, HM/HG degraded to LMWA in 2 h and reached a plateau. Therefore, we employed mass spectrometry (MS) to profile the degraded products of LMWA polymannuronate (PM) and polyguluronate (PG) in more intense conditions. The results indicated that the oxidation process continued until all reducing ends were converted to carboxyl groups. The o-diol could directly oxidize to o-dialdehyde. This study provides a MS based elucidation of the mechanism by which alginate cleaves to oligosaccharides through ozonation.
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Variability in biogenic volatile organic compound (BVOC) emissions across species and seasons poses challenges for accurate regional emission estimates and effective ozone (O3) control policies. To address this issue, we conducted in-situ measurements of emission factors for six dominant tree species in Beijing across four seasons. Subsequently, we developed monthly dynamic standard emission factors (SER-MDs) to model monthly BVOC emissions and their impacts on O3 formation at citywide and district levels. Our observations revealed pronounced seasonal differences in the BVOC composition and emission rates, as well as their responsiveness to monthly average temperature. By introducing the SER-MDs, we estimated BVOC emissions from the dominant tree species in Beijing to be 38.2 Gg yr-1, with monoterpenes and isoprene contributing 49% and 11%, respectively. This calculation reduced the overestimation associated with constant standard emission factors by 31%-38% at district level. The estimates also revealed regional differences in plant compositions rather than simple feedback from regional temperature and photosynthetically active radiation periods. Under these conditions, the maximum monthly BVOC-induced O3 concentration occurred in August and ranged from 4 to 17 µg m-3 across districts, with isoprene being the dominant contributor. Quercus mongolica and Populus tomentosa played significant roles in the formation of BVOC-induced O3 due to their strong isoprene emitting potential in July-August. These results indicate the necessity of introducing species-specific rhythms of BVOC emissions from dominant species in the development of urban BVOC emission inventories. This approach could inform the development of air pollution management policies that are consistent with the local vegetation composition and O3 pollution characteristics. For Beijing and other similar northern cities, reducing the use of tree species emitting substantial amounts of isoprene during periods of regional peak ambient O3 concentrations could constitute an effective nature-based solution for improving urban air quality in the future.
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The ability of air pollution to induce acute exacerbation of asthma is well documented. However, the ability of ozone (O3), the most reactive gaseous component of air pollution, to function as a modulator during sensitization is not well established. C57BL/6 J male mice were intranasally sensitized to house dust mite (HDM) (40 µg/kg) for 3 weeks on alternate days in parallel with once-a-week O3 exposure (1 ppm). Mice were euthanized 24 h following the last HDM challenge. Lung lavage, histology, lung function (both forced oscillation and forced expiration-based), immune cell profiling, inflammation (pulmonary and systemic), and immunoglobulin production were assessed. Compared to HDM alone, HDM + O3 leads to a significant increase in peribronchial inflammation (p < 0.01), perivascular inflammation (p < 0.001) and methacholine-provoked large airway hyperreactivity (p < 0.05). Serum total IgG and IgE and HDM-specific IgG1 were 3-5 times greater in HDM + O3 co-exposure compared to PBS and O3-exposed groups. An increase in activated/mature lung total and monocyte-derived dendritic cells (p < 0.05) as well as T-activated, and T memory lymphocyte subset numbers (p < 0.05) were noted in the HDM + O3 group compared to HDM alone group. Concurrent O3 inhalation and HDM sensitization also caused significantly greater (p < 0.05) lung tissue interleukin-17 pathway gene expression and mediator levels in the serum. Redox imbalance was manifested by impaired lung antioxidant defense and increased oxidants. O3 inhalation during allergic sensitization coalesces in generating a significantly worse TH17 asthmatic phenotype.
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The pursuit of enhanced scientific, refined, and precise ozone and air quality control continues to pose significant challenges. Using data visualization techniques and random forest (RF) algorithms, the temporal distribution of atmospheric pollutants and the interrelationship between O3 concentration and its influential factors were investigated with one-year monitoring data in Deqing county in 2021. The local atmospheric conditions predominantly belonged to NOx-sensitive and transition zone. Extremely high O3 concentration were primarily observed when temperatures (T) exceeded 30 °C, with relative humidity (RH) ranging between 30 and 60 %. NO2, RH and T were identified as the top 3 important factors, and O3 concentration have stronger linearly relationship to RH and T, while stronger nonlinearly relationship to NO2. By employing an optimized RF model, controlling consistent mild and high reaction atmospheric conditions, the O3 concentration response to the change of individual influencing factors was acquired. The O3 concentration increased and then decreased in response to the increasing NO2 concentration, displaying a characteristic inflection point at 10 µg m-3. More reactive radicals produced at higher VOCs concentration and continuing NOx cycle at lower NO2 concentration, resulting in the acceleration in the direction of producing more O3. Therefore, the significant different O3 response to variation of VOCs and NOx concentration between mild and high reaction atmospheric conditions, as well as the existing of oxidant elevation should be considered in local air quality control. This study demonstrates the efficacy of ML methods in simulating nonlinear response of O3, supports the understanding of local O3 formation and quick guidance for precise local O3 pollution control and the related strategies.
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Ambient air pollution has been reported to be a risk factor for hypertensive disorders of pregnancy (HDP). Past studies have reported supportive evidence, but evidence from China is scarce and does not integrate the different periods of the pregnancy course. In this study, 1945 pregnant women with HDP and healthy pregnancies between 2016 and 2022 from the Renmin Hospital of Wuhan University registry network database were analysed. The geographic information, biological information and demographic information of the case were fused in the analysis. Machine learning methods were used to obtain the weight of the variable. Then, we used the generalized linear mixed model to evaluate the relationship between increased exposure to each pollutant at different periods of HDP and examined it in different groups. The results showed that SO2 had the predominate impact (12.65â¯%) on HDP compared with other air pollutants. SO2 exposure was associated with an increased risk of HDP. Increased unit SO2 concentrations were accompanied by an increased risk of HDP (OR = 1.33, 95â¯% CI: 1.13, 1.566), and the susceptible window for this effect was mainly in the first trimester (OR = 1.242, 95â¯% CI: 1.092, 1.412). In addition, SO2 exposure was associated with an increased risk of HDP in urban maternity (OR = 1.356, 95â¯% CI: 1.112, 1.653), obese maternity (OR = 3.58, 95â¯% CI: 1.608, 7.971), no higher education maternity (OR = 1.348, 95â¯% CI: 1.065, 1.706), nonzero delivery maternity (OR = 1.981, 95â¯% CI: 1.439, 2.725), maternal with first time maternity (OR = 1.247, 95â¯% CI: 1.007, 1.544) and other groups. In summary, SO2 exposure in early pregnancy is one of the risk factors for HDP, and the increased risk of HDP due to increased SO2 exposure may be more pronounced in obese, urban, low-education, and nonzero delivery populations.
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While the dominant role of halogens in Arctic ozone loss during spring has been widely studied in the last decades, the impact of sea-ice halogens on surface ozone abundance over the northern hemisphere (NH) mid-latitudes remains unquantified. Here, we use a state-of-the-art global chemistry-climate model including polar halogens (Cl, Br, and I), which reproduces Arctic ozone seasonality, to show that Arctic sea-ice halogens reduce surface ozone in the NH mid-latitudes (47°N to 60°N) by ~11% during spring. This background ozone reduction follows the southward export of ozone-poor and halogen-rich air masses from the Arctic through polar front intrusions toward lower latitudes, reducing the springtime tropospheric ozone column within the NH mid-latitudes by ~4%. Our results also show that the present-day influence of Arctic halogens on surface ozone destruction is comparatively smaller than in preindustrial times driven by changes in the chemical interplay between anthropogenic pollution and natural halogens. We conclude that the impact of Arctic sea-ice halogens on NH mid-latitude ozone abundance should be incorporated into global models to improve the representation of ozone seasonality.
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Surface ozone has become a significant atmospheric pollutant in China, exerting a profound impact on crop production and posing a serious threat to food security. Previous studies have extensively explored the physiological mechanisms of ozone damage to plants. However, the effects of ozone interactions with other environmental factors, such as climate change, on agricultural productivity at the regional scale, particularly under natural conditions, remain insufficiently understood. In this study, we employed an interpretable machine learning framework, specifically the eXtreme Gradient Boosting (XGBoost) algorithm enhanced by SHapley Additive exPlanations (SHAP), to investigate the influence of ozone and its interactions with environmental factors on crop production in China's primary winter wheat region. Additionally, a structural equation model was developed to elucidate the mechanisms driving these interactions. Our findings demonstrate that ozone pollution exerts a significant negative effect on winter wheat productivity (râ¯=â¯-0.47, Pâ¯<â¯0.001), with productivity losses escalating from -12.28â¯% to -22.09â¯% as ozone levels increase. Notably, the impact of ozone is spatially heterogeneous, with western Shandong province identified as a hotspot for ozone-induced damage. Furthermore, our results confirm the complexity of the relationship between ozone pollution and agricultural productivity, which is influenced by multiple interacting environmental factors. Specifically, we found that severe ozone pollution, when combined with high aerosol concentrations or elevated temperatures, significantly exacerbates crop productivity losses, although drought conditions can partially mitigate these adverse effects. Our study highlights the importance of incorporating the interactive effects of air pollution and climate change into future crop models. The comprehensive framework developed in this study, which integrates statistical modeling with explainable machine learning, provides a valuable methodological reference for quantitatively assessing the impact of air pollution on crop productivity at a regional scale.
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Ozone (O3) pollution is usually linked to warm weather and strong solar radiation, making it uncommon in cold winters. However, an unusual occurrence of four high O3 episode days (with maximum hourly concentrations exceeding 100 ppbv and peaking at 121 ppbv) was recorded in January 2018 in Lanzhou city, China. During these episodes, the average daytime concentration of total non-methane volatile organic compounds (TVOCs) reached 153.4 ± 19.0 ppbv, with alkenes-largely emitted from the local petrochemical industry-comprising 82.3 ± 13.1 ppbv. Here we show a photochemical box model coupled with a Master Chemical Mechanism to elucidate the mechanisms behind this unusual wintertime O3 pollution. We find that the typically low temperatures (-1.7 ± 1.3 °C) and weak solar radiation (263.6 ± 60.7 W m- 2) of those winter episode days had a minimal effect on the reactivity of VOCs with OH radicals. Instead, the ozonolysis of alkenes generated Criegee intermediates, which rapidly decomposed into substantial RO x radicals (OH, HO2, and RO2) without sunlight. This radical production led to the oxidation of VOCs, with alkene ozonolysis ultimately contributing to 89.6 ± 8.7% of the O3 formation during these episodes. This mechanism did not activate at night due to the depletion of O3 by the NO titration effect. Furthermore, the findings indicate that a reduction of alkenes by 28.6% or NO x by 27.7% in the early afternoon could significantly mitigate wintertime O3 pollution. Overall, this study unravels the unique mechanism of alkene-induced winter O3 pollution and offers a reference for winter O3 reduction strategies in the petrochemical industrial regions.
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The vertical distribution of ozone (O3) within the boundary layer (BL) and its ground-level effects have been extensively studied. However, observational limitations in obtaining high-resolution, real-time data on O3 and its precursors, especially volatile organic compounds (VOCs), have led to a scarcity of research on O3 formation sensitivity and mechanisms. Online measurements for O3, nitrogen oxides (NO x ), and VOCs were made on the mountainside of Mount Tai (â¼550â m a.s.l.) in China during the summer of 2022 and were compared with the data from a ground-level site. The Master Chemical Mechanism (V3.3.1) was used to uncover a positive correlation between NO x and photochemical reaction rates on the mountainside, marking it as a NO x -limited regime in contrast to the VOC-limited regime identified at surface. On the mountainside, lower NO levels limited hydroxyl radicals (OH) recycling reactions, resulting in earlier O3 peaks and higher concentrations of hydroperoxy radicals (HO2) and organic peroxy radicals (RO2). The arrival of fresh air masses rich in NO accelerated OH radical cycling, enhanced atmospheric oxidization, and significantly impacted surface O3 concentrations though vertical transport. Moreover, NO x reduction scenario simulations show that when considering vertical transport, the peak O3 production rate at the surface is lower due to differences in O3 formation sensitivity vertically. This study highlights the significant sensitivity of O3 formation to NO within the BL, underscoring the potential impact of vertical in situ O3 formation above the ground on surface-level O3 concentrations through vertical exchange, particularly in cities with mountainous terrain.
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In recent years, electrochemical advanced oxidation processes (EAOPs) combined with ozonation have been widely utilized in water/wastewater treatment due to their excellent synergistic effect, high treatment efficiency, and low energy consumption. A comprehensive summary of these ozone-based EAOPs is still insufficient, though some reviews have covered these topics but either focused on a specific integrated process or provided synopses of EAOPs or ozone-based AOPs. This review presents an overview of the fundamentals of several ozone-based EAOPs, focusing on process optimization, electrode selection, and typical reactor designs. Additionally, the service life of electrodes and improvement strategies for the stability of ozone-based EAOPs that are ignored by previous reviews are discussed. Furthermore, four main application fields are summarized, including disinfection, emerging contaminants treatment, industrial wastewater treatment, and resource recovery. Finally, the summary and perspective on ozone-based EAOPs are proposed. This review provides an overall summary that would help to gain insight into the ozone-based EAOPs to improve their environmental applications.
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This study aimed to determine the effect of ozone on the expression of Bax and Bcl-2 genes in dental pulp cells. Additionally, the programmed cell death protein 1, programmed death-ligand 1, and CD200 antigens were determined in lymphocytes to assess their surface expression. Dental pulp cells were cultured from extracted healthy third molars and characterized as dental pulp stromal cells. Gene expression of Bcl-2 and Bax was analyzed at 0 s, 6 s, and 12 s of ozone exposure using real-time PCR. Lymphocytes from dental pulp were subjected to ozone exposure for 12 s and PD-1, PD-L1, and CD200/CD200R expression was analyzed by flow cytometry. Upon exposure to ozone for 6 s, the Bcl-2 expression decreased significantly to -0.09, and at 12 s, it increased significantly to 0.3. Bax gene expression level increased significantly to 0.188 after 6 s exposure, and at 12 s, to 0.16. Lymphocytes exposed to ozone for 12 s showed minimal changes in PD-1, PD-L1, and CD200/CD200R expression levels, indicating that oxidative stress does not impact the signaling pathways regulating these molecules. The significant upregulation of Bcl-2 at 12 s highlights the cells' effort to protect themselves from prolonged oxidative stress, possibly tipping the balance toward cell survival and tissue repair. However, the absence of changes in PD-1 and PD-L1 expression on lymphocytes under oxidative stress suggests that these molecules are not sensitive to oxidative stress in this context.