Single Droplet Tweezer Revealing the Reaction Mechanism of Mn(II)-Catalyzed SO2 Oxidation.

Sulfate aerosol is one of the major components of secondary fine particulate matter in urban haze that has crucial impacts on the social economy and public health. Among the atmospheric sulfate sources, Mn(II)-catalyzed SO2 oxidation on aerosol surfaces has been regarded as a dominating one. In this work, we measured the reaction kinetics of Mn(II)-catalyzed SO2 oxidation in single droplets using an aerosol optical tweezer. We show that the SO2 oxidation occurs at the Mn(II)-active sites on the aerosol surface, per a piecewise kinetic formulation, one that is characterized by a threshold surface Mn(II) concentration and gaseous SO2 concentration. When the surface Mn(II) concentration is lower than the threshold value, the reaction rate is first order with respect to both Mn(II) and SO2, agreeing with our traditional knowledge. But when surface Mn(II) concentration is above the threshold, the reaction rate becomes independent of Mn(II) concentration, and the reaction order with respect to SO2 becomes greater than unity. The measured reaction rate can serve as a tool to estimate sulfate formation based on field observation, and our established parametrization corrects these calculations. This framework for reaction kinetics and parametrization holds promising potential for generalization to various heterogeneous reaction pathways.

Insights into the Formation Mechanism of Reactive Oxygen Species in the Interface Reaction of SO2 on Hematite.

The interplay between sulfur and iron holds significant importance in their atmospheric cycle, yet a complete understanding of their coupling mechanism remains elusive. This investigation delves comprehensively into the evolution of reactive oxygen species (ROS) during the interfacial reactions involving sulfur dioxide (SO2) and iron oxides under varying relative humidity conditions. Notably, the direct activation of water by iron oxide was observed to generate a surface hydroxyl radical (•OH). In comparison, the aging of SO2 was found to markedly augment the production of •OH radicals on the surface of α-Fe2O3 under humid conditions. This augmentation was ascribed to the generation of superoxide radicals (•O2-) stemming from the activation of O2 through the Fe(II)/Fe(III) cycle and its combination with the H+ ion to produce hydrogen peroxide (H2O2) on the acidic surface. Moreover, the identification of moderate relative humidity as a pivotal factor in sustaining the surface acidity of iron oxide during SO2 aging underscores its crucial role in the coupling of iron dissolution, ROS production, and SO2 oxidation. Consequently, the interfacial reactions between SO2 and iron oxides under humid conditions are elucidated as atmospheric processes that enhance oxidation capacity rather than deplete ROS. These revelations offer novel insights into the mechanisms underlying •OH radical generation and oxidative potential within atmospheric interfacial chemistry.

Multiple Sulfur Isotopic Evidence for Sulfate Formation in Haze Pollution.

The mechanism of sulfate formation during winter haze events in North China remains largely elusive. In this study, the multiple sulfur isotopic composition of sulfate in different grain-size aerosol fractions collected seasonally from sampling sites in rural, suburban, urban, industrial, and coastal areas of North China are used to constrain the mechanism of SO2 oxidation at different levels of air pollution. The Δ33S values of sulfate in aerosols show an obvious seasonal variation, except for those samples collected in the rural area. The positive Δ33S signatures (0‰ < Δ33S < 0.439‰) observed on clean days are mainly influenced by tropospheric SO2 oxidation and stratospheric SO2 photolysis. The negative Δ33S signatures (-0.236‰ < Δ33S < ∼0‰) observed during winter haze events (PM2.5 > 200 µg/m3) are mainly attributed to SO2 oxidation by H2O2 and transition metal ion catalysis (TMI) in the troposphere. These results reveal that both the H2O2 and TMI pathways play critical roles in sulfate formation during haze events in North China. Additionally, these new data provide evidence that the tropospheric oxidation of SO2 can produce significant negative Δ33S values in sulfate aerosols.

Oxalate-Promoted SO2 Uptake and Oxidation on Iron Minerals: Implications for Secondary Sulfate Aerosol Formation.

Mineral dust serves as a significant source of sulfate aerosols by mediating heterogeneous sulfur dioxide (SO2) oxidation in the atmosphere. Given that a considerable proportion of small organic acids are deposited onto mineral dust via long-range transportation, understanding their impact on atmospheric SO2 transformation and sulfate formation is of great importance. This study investigates the effect of oxalate on heterogeneous SO2 uptake and oxidation phenomenon by in situ FTIR, theoretical calculation, and continuous stream experiments, exploiting hematite (Fe2O3) as an environmental indicator. The results highlight the critical role of naturally deposited oxalate in mononuclear monodentate coordinating surface Fe atoms of Fe2O3 that enhances the activation of O2 for oxidizing SO2 into sulfate. Meanwhile, oxalate increases the hygroscopicity of Fe2O3, facilitating H2O dissociation into reactive hydroxyl groups and further augmenting the SO2 uptake capacity of Fe2O3. More importantly, other conventional iron minerals, such as goethite and magnetite, as well as authentic iron-containing mineral dust, exhibit similar oxalate-promoted sulfate accumulation behaviors. Our findings suggest that oxalate-assisted SO2 oxidation on iron minerals is one of the important contributors to secondary sulfate aerosols, especially during the nighttime with high relative humidity.

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2.

Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO2, which produces SO3 and subsequently H2SO4, an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work, the kinetics of the reactions of dimethyl substituted Criegee intermediate (CH3)2COO with water vapor and with SO2 were directly measured via UV absorption of (CH3)2COO under near-atmospheric conditions. The results indicate that (i) the water reaction with (CH3)2COO is not fast enough (kH2O < 1.5 × 10(-16) cm(3) s(-1)) to consume atmospheric (CH3)2COO significantly and (ii) (CH3)2COO reacts with SO2 at a near-gas-kinetic-limit rate (kSO2 = 1.3 × 10(-10) cm(3) s(-1)). These observations imply a significant fraction of atmospheric (CH3)2COO may survive under humid conditions and react with SO2, very different from the case of the simplest Criegee intermediate CH2OO, in which the reaction with water dimer predominates in the CH2OO decay under typical tropospheric conditions. In addition, a significant pressure dependence was observed for the reaction of (CH3)2COO with SO2, suggesting the use of low pressure rate may underestimate the impact of this reaction. This work demonstrates that the reactivity of a Criegee intermediate toward water vapor strongly depends on its structure, which will influence the main decay pathways and steady-state concentrations for various Criegee intermediates in the atmosphere.

Evaluation of sulfur trioxide detection with online isopropanol absorption method.

Measurement of the SO3 concentration in flue gas is important to estimate the acid dew point and to control corrosion of downstream equipment. SO3 measurement is a difficult question since SO3 is a highly reactive gas, and its concentration is generally two orders of magnitude lower than the SO2 concentration. The SO3 concentration can be measured online by the isopropanol absorption method; however, the reliability of the test results is relatively low. This work aims to find the error sources and to evaluate the extent of influence of each factor on the measurement results. The test results from a SO3 analyzer showed that the measuring errors are mainly caused by the gas-liquid flow ratio, SO2 oxidation, and the side reactions of SO3. The error in the gas sampling rate is generally less than 13%. The isopropanol solution flow rate decreases 3% to 30% due to the volatilization of isopropanol, and accordingly, this will increase the apparent SO3 concentration. The amount of SO2 oxidation is linearly related to the SO2 concentration. The side reactions of SO3 reduce the selectivity of SO42- to nearly 73%. As sampling temperature increases from 180 to 300°C, the selectivity of SO42- decreases from 73% to 50%. The presence of H2O in the sample gas helps to reduce the measurement error by inhibiting the volatilization of the isopropanol and weakening side reactions. A formula was established to modify the displayed value, and the measurement error was reduced from 25%-54% to less than 15%.

Homogeneous oxidation of SO2 in the tail gas incinerator of sulfur recovery unit.

The formation and emission of sulfur trioxide (SO3) in sulfur recovery unit has received increasing attention due to its adverse effects on the operation of plant and environment. Due to the excess oxygen, high concentration of SO2 and high temperature, SO3 formation in the sulfur recovery unit tail gas incinerator may significantly increase. A small horizontal tube reactor was employed to simulate the homogeneous oxidation of SO2 in the tail gas incinerator. The SO3 concentration was measured with a controlled condensation method at the outlet of the reactor. The present work focuses on the gas-phase chemistry and examines the impact of different combustion parameters and atmospheres on the formation of SO3 in the tail gas incinerator. Experiment results show that the increased O2 and SO2 concentrations along with increasing temperature are favorable for enhancing SO3 formation over the range of tested parameters. The presence of water vapor has an enhancing effect of SO2 oxidation in the experiments conducted. No significant effect of CO2 was found to the oxidation of SO2.

High-throughput technology for novel SO2 oxidation catalysts.

We review the state of the art and explain the need for better SO2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO2 to SO3. High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations.

Brown carbon: An underlying driving force for rapid atmospheric sulfate formation and haze event.

The rapid sulfate formation is a crucial factor determining the explosive growth of fine particles and the frequent occurrence of severe haze events in China. Recent field observations also show that brown carbon is one of the most critical components in aerosol particles sampled during haze episodes. To this day, there is limited knowledge that accesses the role of brown carbon in atmospheric chemistry. In fact, these carbonaceous particulate matters, mainly derived from forest fires, biomass burning, and biogenic release, can act as photosensitizers and produce varieties of active intermediates to alter oxidation capacity. Experimental results in this work provide evidence that hydroxyl radical (∙OH) stems from brown carbon proxies fulvic acid /humic acid (FA/HA) upon irradiation, leading to rapid SO2 oxidation on brown carbon particles in the atmosphere. Further correlation analyses for sulfate formation and chromophore properties of 12 model compounds demonstrate that brown carbon particles with higher aromaticity and E2/E3 (the ratio of absorbance at 254 nm to that at 365 nm) would facilitate ∙OH production and SO2 photo-oxidation. Uptake coefficient measurements and sulfate production rate estimation indicate that brown carbon could gain importance in atmospheric SO2 oxidation. A better understanding of SO2 uptake kinetics on brown carbon surfaces favors in defining new regulations to improve air quality and reduce the harmful effects of haze events on resident health and the environment.

Hydrotalcite-based CeNiAl mixed oxides for SO2 adsorption and oxidation.

The impact of Ce on SO2 adsoption and oxidation was studied over a series of flower-like hydrotalcite-based CeNiAl mixed oxides. Combined with XRD, BET, pyridine chemisorption, CO2-TPD, XPS and H2-TPR results, it revealed that introduction of Ce into NiAlO generates new centres for oxygen storage and release, promotes the enhancement of Lewis acid strength, increases weakly and strongly alkaline sites, and increases ability for SO2 adsorption and oxidation. Furthermore, in situ Fourier transform infrared spectroscopy revealed that adsorbed SO2 molecules formed surface bidentate binuclear sulfate. Taken together, we propose that the addition of Ce4+ to NiAlO acts to improve this compound as major adsorbent for SO2.

Oxidation of SO2 over C-doped boron nitride nanosheets: The role of C-doping, and solvent effects.

In this work, density functional theory calculations are performed to examine the catalytic oxidation of SO2 in the presence of O2 molecule over carbon-doped hexagonal boron nitride nanosheets (h-BNNSs). The SO2 oxidation over these surfaces is characterized as a two-step mechanism; (a) SO2 + O2 → SO3 + O* and (b) SO2 + O* → SO3. According to the obtained results, the activation energies and reaction mechanism depend greatly on the substitution site of the C-doped h-BNNS. That is, the catalytic activity of C atom located on top of the B-vacancy site of h-BNNS is larger than that of on top of the N-vacancy. Moreover, it is found that the energy barriers for the oxidation of SO2 are considerably decreased in an aqueous solution. For a given substrate, the activation energy for the oxidation of H2SO3 is much larger than that of SO2, suggesting that the direct conversion of SO2 to SO3 should be the main reaction pathway for the oxidation of SO2. The results of present study could contribute to design highly active BN-based catalysts to oxidize SO2 molecule.