SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism.

Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of (32)SO2, (33)SO2, (34)SO2, and (36)SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ(33)S/δ(34)S and Δ(36)S/Δ(33)S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events.

Determination of the photolysis rate coefficient of monochlorodimethyl sulfide (MClDMS) in the atmosphere and its implications for the enhancement of SO2 production from the DMS + Cl2 reaction.

In this work, the photolysis rate coefficient of CH3SCH2Cl (MClDMS) in the lower atmosphere has been determined and has been used in a marine boundary layer (MBL) box model to determine the enhancement of SO2 production arising from the reaction DMS + Cl2. Absorption cross sections measured in the 28000-34000 cm(-1) region have been used to determine photolysis rate coefficients of MClDMS in the troposphere at 10 solar zenith angles (SZAs). These have been used to determine the lifetimes of MClDMS in the troposphere. At 0° SZA, a photolysis lifetime of 3-4 h has been obtained. The results show that the photolysis lifetime of MClDMS is significantly smaller than the lifetimes with respect to reaction with OH (≈ 4.6 days) and with Cl atoms (≈ 1.2 days). It has also been shown, using experimentally derived dissociation energies with supporting quantum-chemical calculations, that the dominant photodissocation route of MClDMS is dissociation of the C-S bond to give CH3S and CH2Cl. MBL box modeling calculations show that buildup of MClDMS at night from the Cl2 + DMS reaction leads to enhanced SO2 production during the day. The extra SO2 arises from photolysis of MClDMS to give CH3S and CH2Cl, followed by subsequent oxidation of CH3S.

Experimental study on removals of SO2 and NO(x) using adsorption of activated carbon/microwave desorption.

UNLABELLED: Experimental studies on desulfurization and denitrification were carried out using activated carbon irradiated by microwave. The influences of the concentrations of nitric oxide (NO) and sulfur dioxide (SO2), the flue gas coexisting compositions, on adsorption properties of activated carbon and efficiencies of desulfurization and denitrification were investigated. The results show that adsorption capacity and removal efficiency of NO decrease with the increasing of SO2 concentrations in flue gas; adsorption capacity of NO increases slightly first and drops to 12.79 mg/g, and desulfurization efficiency descends with the increasing SO2 concentrations. Adsorption capacity of SO2 declines with the increasing of O2 content in flue gas, but adsorption capacity of NO increases, and removal efficiencies of NO and SO2 could be larger than 99%. Adsorption capacity of NO declines with the increase of moisture in the flue gas, but adsorption capacity of SO2 increases and removal efficiencies of NO and SO2 would be relatively stable. Adsorption capacities of both NO and SO2 decrease with the increasing of CO2 content; efficiencies of desulfurization and denitrification augment at the beginning stage, then start to fall when CO2 content exceeds 12.4%. The mechanisms of this process are also discussed. IMPLICATIONS: The prominent SO2 and NOx treatment techniques in power plants are wet flue gas desulfurization (FGD) and the catalytic decomposition method like selective catalytic reduction (SCR) or nonselective catalytic reduction (NSCR). However, these processes would have some difficulties in commercial application due to their high investment, requirement of expensive catalysts and large-scale equipment, and so on. A simple SO2 and NOx reduction utilizing decomposition by microwave energy method can be used. The pollutants control of flue gas in the power plants by the method of microwave-induced decomposition using adsorption of activated carbon/microwave desorption can meet the requirements of environmental protection, which will be stricter in the future.

Simultaneous SO2 and NO removal from flue gas based on TiO2 photocatalytic oxidation.

A new approach to the simultaneous removal of SO2 and NO from flue gas, by TiO2 photocatalysis based on UV irradiation technology, is presented. Experiments on the simultaneous desulphurization and denitrification were carried out using this photocatalyst in a self-designed photocatalytic reactor. Under the optimal experimental conditions, a removal efficiency of 98% for SO2 and 50% for NO was achieved. Scanning electron microscopy, transmission electron microscopy and X-ray energy spectrometry were used to observe the surface characteristics of the TiO2 photocatalyst. It was found that the surface of the quartz sand carrier was covered with Ti, on which the Si content of the quartz sand carrier was similar to the Ti content, indicating that the quartz sand supported the TiO2 membrane well. Based on the results of X-ray photoelectron spectroscopy (XPS) and chemical analysis of the resulting products, the SO2 and NO removal mechanisms were revealed. Sulphate was the main desulphurization product and nitrite was the main denitrification product. In the removal reaction, NO was rapidly oxidized to NO2 and absorbed in the chemical reaction.

Photocatalytic degradation of NOx gases using TiO2-containing paint: a real scale study.

An indoor car park was appropriately equipped in order to test the de-polluting efficiency of a TiO(2)-containing paint in an indoor polluted environment, under real scale configuration. Depollution tests were performed in an artificially closed area of the parking, which was polluted by a car exhaust during the testing period. The ceiling surface of the car park was covered with white acrylic TiO(2)-containing paint (PP), which was developed in the frame of the EU project 'PICADA' (Photocatalytic Innovative Coverings Application for Depollution Assessment). The closed area was fed with car exhaust gases. As soon as the system reached steady state, the UV lamps were turned on for 5h. The difference between the final and the initial steady state concentration indicates the removal of the pollutants due to both the photocatalytic paint and car emission reduction. Results showed a significant photocatalytic oxidation of NO(x) gases. The photocatalytic removal of NO and NO(2) was calculated to 19% and 20%, respectively, while the photocatalytic rate (microgm(-2)s(-1)) ranged between 0.05 and 0.13 for NO and between 0.09 and 0.16 for NO(2).

The use of vacuum ultraviolet irradiation to oxidize SO2 and NOx for simultaneous desulfurization and denitrification.

A simple and efficient method for simultaneous desulfurization and denitrification via vacuum ultraviolet (VUV) irradiation and with no additional chemicals is presented. The simultaneous removal of 90% SO2 and 96% NOx (NO+NO2) was achieved from the simulated flue gas under the irradiation from a low-pressure mercury lamp with main wavelengths of 185 and 254 nm, respectively. The composition, flow rate, and temperature of the simulated flue gas, as well as the VUV light intensity, were evaluated as the factors impacting on the efficiency of SO2 and NOx removal. The OH, HO2, O, and O3 produced from the photolysis of H2O and O2 were concluded as the major reactive oxygen species that oxidized SO2 and NOx. The additional OH and HO2 generated through the reactions of NO+HO2 and SO2+OH/HO2 improved treatment efficiency, while the oxidation products of NOx, e.g., NO2, HNO2, HNO3, and HNO4, consumed massive reactive oxygen species (such as O, OH, and HO2) and thereby reducing the removal efficiencies. The main reaction products were characterized as H2SO4 and HNO3 by ion chromatography, which could be used as chemical or fertilizer raw materials.

Dissociation of sulfur dioxide by ultraviolet multiphoton absorption between 224 and 232 nm.

Multiphoton excitation and dissociation of SO(2) have been investigated in the wavelength range from 224 to 232 nm. Strong evidence is found for two-photon excitation to the H Rydberg state, followed by dissociation to SO + O and ionization of the SO product by absorption of a third photon. The two-photon excitation is resonantly enhanced via the C (1)B(2) intermediate state, and the two-photon yield spectrum thus bears a strong resemblance to the spectrum of this intermediate. Imaging of the O((3)P(2)), S((1)D(2)), and SO products suggests that, following dissociation of SO(2) from the H state, SO is produced in the A and B electronic states. S((1)D(2)) is produced both from two-photon dissociation of SO(2) to give S((1)D(2)) + O(2) and by single-photon dissociation of SO(+). In the former process, the O(2) is likely formed in all of its lowest three electronic states.

Studies on photochemical reactions of air pollutants. XIV.Photooxidation of sulfur dioxide in air by various air pollutants.

Upon exposure to sunlight, or to artificial light at wavelengths longer than 290 nm, sulfur dioxide in air underwent oxidation to give sulfur trioxide in the presence of air pollutants such as biacetyl (2,3-butanedione), benzaldehyde and nitrogen dioxide, but not in their absence. Only nitrogen dioxide completely oxidized sulfur dioxide to sulfur trioxide.