Transport and oxidation of SO2 in a stagnant foggy valley

The fate of SO₂ emitted in the San Joaquin Valley of California under stagnant foggy conditions was determined by the release of an inert tracer and the concurrent monitoring of SO₂ and SO₄²⁻ concentrations. At night, SO₂ was found to be trapped in a dense fog layer below a strong and persistent inversion based a few hundred meters above the valley floor. This lack of ventilation led to the accumulation of SO₂ and SO₄²⁻ over a major SO₂ source region in the valley. The rate of oxidation of SO₂ to SO₄²⁻ in fog was estimated at 3 ± 2%h⁻¹. Production of acidity from the oxidation of SO₂ fully titrated the NH₃(g) present before the fog, and led to a progressive drop of the fogwater pH over the course of the night. In the afternoon, the valley was found to be efficiently ventilated by a buoyant upslope flow through the inversion. The tracer data indicated that about 40 % of the air transported upslope in the afternoon was returned to the valley in the night-time drainage flow. The fates of SO₂ and SO₄²⁻ in the valley during extended highinversion episodes appear to depend considerably on the presence of fog or stratus, and on the extent of daytime insolation.     

Rainborne SO2, precipitation pH and airborne SO2 over short sampling times throughout individual events

Sequential samples of rain, over periods as short as a few minutes, were collected from nine individual events in East Anglia (U.K.). Rainborne SO₂ and rainfall pH was determined and atmospheric SO₂ was measured on a 15-mm basis. A much better agreement was found between observed SO₂ washout ratios and those predicted from equilibrium theory than in previous studies when the sampling was over longer time-bases. The rainborne SO₂ concentrations and pH values exhibit considerable variation, on a time-scale of a few minutes, throughout individual events.     

Evaluation of the DMS flux and its conversion to SO2 over the southern ocean

A total of 16 boundary layer (BL) DMS flux values were derived from flights over the Southern Ocean. DMS flux values were derived from airborne observations recorded during the Aerosol Characterization Experiment (ACE 1). The latitude range covered was 55°S–40°S. The method of evaluation was based on the mass-balance photochemical-modeling (MBPCM) approach. The estimated flux for the above latitude range was 0.4–7.0 μmol m⁻² d⁻¹. The average value from all data analyzed was 2.6±1.8 μmol m⁻² d⁻¹. A comparison of the MBPCM methodology with several other DMS flux methods (e.g., ship and airborne based) revealed reasonably good agreement in some cases and significant disagreement in other cases. Considering the limited number of cases compared and the fact that conditions for the comparisons were far from ideal, it is not possible to conclude that major agreement or differences have been established between these methods. A major result from this study was the finding that DMS oxidation is a major source of BL SO₂ over the Southern Ocean. Model simulations suggest that, on average, the conversion efficiency is 0.7 or higher, given a lifetime for SO₂ of ∼1 d. A comparison of two sulfur case studies, one based on DMS–SO₂ data generated on the NCAR C-130 aircraft, the other based on data recorded on the NOAA ship Discoverer, revealed qualitative agreement in finding that DMS was a major source of Southern Ocean SO_2. On the other hand, significant disagreement was found regarding the DMS/SO₂ conversion efficiency (e.g., 0.3–0.5 versus 0.7–0.9). Although yet unknown factors, such as vertical mixing, may be involved in reducing the level of disagreement, it does appear at this time that some significant portion of this difference may be related to systematic differences in the two different techniques employed to measure SO₂. It would seem prudent, therefore, that further instrument intercomparison SO₂ studies be considered. It also would be desirable to stage new intercomparison activity between the MBPCM flux approach and the air-to-sea gradient as well as other flux methods, but under far more favorable conditions.     

Humidity effects on photochemical aerosol formation in the SO2-NO-C3H6-air system

In order to investigate the effects of humidity on the gas-phase oxidation of SO₂ in polluted air and on the subsequent aerosol formation process, photoirradiation experiments were carried out by means of a 4-m³ chamber, in which mixtures containing SO₂, NO and C₃H₆ with concentrations in the ppm range were exposed to simulated solar radiation in different relative humidity (r.h.) conditions. The total amount of oxidized SO₂ was quantified from the SO₄²⁻ yield determined by the chemical analysis of the aerosol product, and a part due to the oxidation by the OH radical was evaluated by estimating the OH concentration from the decay rate of C₃H₆. The remaining part was assigned to the oxidation by the Criegee intermediate, as it had a good correlation with the progress of the O₃ + C₃H₆ reaction. The contributions of the two oxidizing species to the total conversion and the oxidation rate of SO₂ were measured as functions of r.h. As a result, experimental evidence was obtained for the prediction of Calvert and Stockwell's (1983, Envir. Sci. Technol. 17, 428A–443A) simulation that the oxidation due to the Criegee intermediate was retarded by the increase in humidity. The OH contribution, on the other hand, was almost independent of r.h. It was observed consequently that the total oxidized amount of SO₂ considerably decreased as r.h. was higher.The humidity effect on the aerosol formation process was found to be more complicated than the effect on the gas-phase chemistry. The maximum rate of increase in the particle number concentration rose linearly with increasing r.h., but the number concentration itself measured at its maximum or at the end of the irradiation reached a ceiling value around r.h. = 30% and went down for higher r.h. The average panicle size in the final stage of the reaction showed a minimum around the same r.h. at which the number concentration was maximum. The H₂SO₄ concentration in the mist particles, however, decreased monotonically as r.h. got higher. It was suggested that these different responses against the increase in humidity resulted from the cooperation of several processes such as the H₂SO₄ monomer formation, the H₂O condensation, the particle coagulation, etc., which had different dependences on r.h.     

Transport and chemical composition of the summer aerosol in the Norwegian Arctic

The chemical composition and transfer routes of the Arctic aerosol during summer have been studied at Ny-Alesund, Bjørnøya, Hopen and Jan Mayen in the period August/September 1983. Samples were also collected on mainland Norway to assess the origin of aerosols transported to the Norwegian Arctic. The concentrations of Si, Al, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Pb, Zn and Cu were measured in samples from a six-stage cascade impactor of Battelle design by particle-induced X-ray emissions (PIXE). The concentrations of Cd, Ni, Pb and Zn were also measured in samples from high-volume samplers by atomic absorption spectrophotometry (AAS).Three interesting periods were identified from the element concentrations. At the beginning of the measurement campaign, the air pollutants measured at Ny-Alesund and Hopen most likely originated in northern America and Greenland. A few days later, very high concentrations of Cd and Zn at Ny-Alesund seemed to be due to air mass transfer from the Soviet Union. During the last episode, observed at Ny-Alesund and Hopen in September, elevated concentrations of several anthropogenic pollutants appeared to be due to emissions in Europe.The results show that anthropogenic emissions from sources in western Europe, Eurasia and northern America may pollute the Arctic air not only in winter but in summer as well. Present levels of air pollutants in the Norwegian Arctic in summer are within the range of levels observed in other remote regions, but are one order of magnitude higher than in Antarctica.     

Evaluation of SO2 dry deposition over short vegetation in Portugal

SO₂ dry deposition was studied over short vegetation, in Portugal, by means of the concentration gradient method. The experimental study involved one first phase of long-term measurements carried out in a grassland and, subsequently, a second period of several 1997 intensive field campaigns performed in three places representing different climate and surface conditions. Temporal and spatial patterns of dry deposition parameters show that downward fluxes of SO₂ are by some extent affected by surface processes. Median R_c varied from 140 s cm⁻¹ to values around 200 s cm⁻¹, in a wide range of environmental conditions. Stomatal uptake is an important sink when vegetation is biologically active, but its contribution is effectively low when compared with non-stomatal mechanisms, especially when the surface is wet. Under dry conditions R_c increases by a factor of two, but SO₂ deposition rates then still are significant. The parameterisation of the surface resistance for SO₂ proved to be difficult, but V_d derived with the Erisman parameterisation (Erisman et al., Atmos. Environ. 28 (16) (1994) 2595) compared best with measured values, at low time resolution scale and especially under moisture conditions.     

Long-term measurements of SO2 dry deposition over Gansu Province,China

Potassium carbonate sulfation plates, monitored monthly for 11 years from 48 sites in 11 cities in Gansu Province, China, provide a crude estimate of cumulative SO₂ dry depositions. Measured SO₂ dry deposition rates were 1.6–472 mg m⁻² day⁻¹ and had seasonal variations with maxima in winter and minima mainly during summer as a result of higher winter and lower summer SO₂ concentrations. The 11-year monthly average SO₂ dry deposition rates are 23.2–248.97 and 11.7–175.6 mg m⁻² day⁻¹ in the eleven cities in winter and summer, respectively. A monthly average SO₂ deposition velocity was also estimated from 0.06 to 9.72 cm s⁻² in the 11 cities studied with a 11-year average maximum value of about 1.1–2.7 cm s⁻² in April and July and a 11-year average minimum value of about 0.2–1.0 cm s⁻¹ in January. The SO₂ dry deposition velocity also exhibits an increasing with wind speed in basins of less than 500 mm annual precipitation. In contrast, due to influences of the relative humidity in valleys of more than 500 mm annual precipitation, it shows a decreasing trend with wind speed increasing.     

SO2 oxidation in cloud drops containing NaCl or sea salt as condensation nuclei

Experimental results from cloud-chamber studies provide direct evidence that NaCl, artificial sea salt and natural sea salt promote faster rates of aqueous SO₂ oxidation than observed in the absence of these salts. However, the chemical basis for this effect has not been clarified. Oxidation rates > 30% h⁻¹are observed in cloud-chamber experiments with 0.4 μm-diameter salt particles as cloud nuclei and a cloud pH of 6. SO₂ oxidation under similar atmospheric conditions might account for the rapid formation of sulfate observed in marine fogs.     

Trace elements and sea salt aerosols over the sea areas around the Indian sub-continent

The nature and the characteristics of trace elements and sea salt aerosols in the ocean atmosphere around the Indian sub-continent was studied. For this purpose, concentrations of the total suspended particulates (TSP) as well as of its various chemical components together with their mass size distributions were measured on 11 days in May 1983. Over the sea regions around the sub-continent, sampling was done on board the research Vessel Gaveshani using a high volume air sampler and a multistage Andersen sampler. The concentrations of soil-origin elements (Al, Fe, Mn and Ca) were found to be at a maximum over the Arabian sea region suggesting the presence of dust particulates, transported from the Arabian peninsula. The near sea water ratio of CI/ Na was observed in giant size (> 2.5 μm dia) sea salt aerosols suggested that there was very little fractionation in these aerosols. The ratio value considerably decreased in the case of sub-μm sea salt particles. The chemical components originating from soil and from sea salt showed a unimodal distribution whereas those from anthropogenic sources showed a bimodal distribution.     

Modelling changes of aerosol compositions over Belgium and Europe

Seasonal changes in aerosol compositions over Belgium and Europe are simulated with an extended version of the EUROS model. EUROS is capable of modelling mass and chemical composition of aerosols in two size fractions (PM_2.5 and PM_10-2.5). The chemical composition is expressed in terms of seven components: ammonium, nitrate, sulphate, primary inorganic compounds, elementary carbon, primary organic compounds and Secondary Organic Compounds (SOA). A comparison of modelled and measured aerosol concentrations showed that modelled concentrations are generally consistent with observed concentrations. The chemical composition of the aerosol showed a strong dependence on the season. High aerosol concentrations during the summer were mainly due to high concentrations of the secondary components nitrate, ammonium, sulphate and SOA in the size fraction PM_2.5. In contrast, during autumn and winter, increased PM-concentrations were mainly due to higher concentrations of primary components, especially in the size fraction PM_10-2.5.     

Heterogeneous loss of HO2 by KCl,synthetic sea salt,and natural seawater aerosol particles

The HO₂ uptake to aerosol particles is potentially significant sink for the HO₂ radical in the marine atmosphere. To assess the heterogeneous loss of HO₂ on marine aerosol particles, we have investigated the uptake coefficients (γ) of HO₂ for submicron aerosol particles of KCl, synthetic sea salt, and natural seawater under ambient conditions (760 Torr and 296 ± 2 K) using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. γ values determined for dry and wet aerosols of KCl were 0.02 ± 0.01 and 0.07 ± 0.03 at 66% and 75% RH, respectively, while γ values for those doped with CuSO₄ was 0.55 ± 0.19 at 75% RH. γ values determined for synthetic sea-salt particles were 0.07 ± 0.03, 0.12 ± 0.04 and 0.13 ± 0.04 at 35%, 50%, 75% RH, respectively, while γ values for natural seawater particles were 0.10 ± 0.03, 0.11 ± 0.02 and 0.10 ± 0.03 at 35%, 50%, 75% RH, respectively. We recommend a HO₂ uptake coefficient in marine areas of 0.1 for modeling and estimated the contribution of heterogeneous loss of HO₂ by sea-salt aerosol particles in marine areas using a box model. Our box-model simulations suggested that daytime maximum HO₂ concentrations decreased to 87–94% of the values without heterogeneous loss.     

在Ru/Al2O3催化剂上用H2对SO2选择性催化还原的研究

本文对用H2来使SO2选择性催化还原为单质硫在Ru/Al2O3催化剂上的行为进行研究.当物料比经过优化确定为SO2/H2=12.8时,在500℃下,SO2的转化率为90%以上,单质硫的产率为70%左右.比较于其他的催化还原SO2的催化剂,本催化剂采用金属而不是金属硫化物,这样既省去了催化剂预硫化的过程,同时也使在有氧条件下的选择性催化还原成为可能.实验考察了O2及水蒸气存在对过程的影响.在实验过程中发现,H2S作为中间产物生成,可推论该过程在催化剂上分两步进行SO2首先在催化剂金属上被H2深度还原为H2S,然后在Al2O3载体的酸性中心上SO2与H2S发生Claus反应产生单质硫.     

Atmospheric aerosol measurements over North America and the North Atlantic Ocean

Measurements of atmospheric aerosol, obtained during thirty-nine transit flights within North America and across the North Atlantic Ocean, are presented and analyzed. The measurements comprise Aitken nucleus concentrations, particle size distributions, and the particle component of the light-scattering coefficient. Measurements of ozone are also presented.These data provide information on the ‘background’ and average values of the atmospheric aerosol in the lower and middle troposphere in continental, marine and high-latitude airmasses. The effects of temperature inversions, vertical mixing, clouds and precipitation, and stratospheric intrusions are illustrated. Time and spatial scales are derived for the transformations of the aerosol from those characteristic of a marine airmass into those characteristic of a continental airmass and vice versa.     

Marine sulfur cycling and the atmospheric aerosol over the springtime North Atlantic

We investigated the distribution of phytoplankton species and the associated dimethyl sulfur species, dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) on a cruise into the spring bloom region of the northern North Atlantic (near 47 degrees N, 19 degrees W). The cruise was timed to characterize the relationship between plankton dynamics and sulfur species production during the spring plankton bloom period. At the same time, we measured the DMS concentrations in the atmospheric boundary layer and determined the abundance and composition of the atmospheric aerosol.The water column studies showed that the interplay of wind-driven mixing and stratification due to solar heating controlled the evolution of the plankton population, and consequently the abundance of particulate and dissolved DMSP and DMS. The sea-to-air transfer of DMS was modulated by strong variations in wind speed, and was found to be consistent with currently available transfer parameterizations. The atmospheric concentration of DMS was strongly dependent on the sea surface emission, the depth of the atmospheric boundary layer and the rate of photooxidation as inferred from UV irradiance. Sea-salt and anthropogenic sulfate were the most abundant components of the atmospheric aerosol. On two days, a strong dust episode was observed bringing mineral dust aerosol from the Sahara desert to our northerly study region. The background concentrations of marine biogenic sulfate aerosol were low, near 30-60 ppt. These values were consistent with the rate of sulfate production estimated from the abundance of DMS in the marine boundary layer.     

Sensitivity of Native Desert Vegetation To SO2 and to SO2 and NO2 Combined

Interest in air pollution injury to native vegetation has been generated with the construction and planned construction of large coal-fired power plants near the coal reserves in the southwest desert areas of the United States. Since information on the effects of SO₂ on these native species was not available in the literature, fumigation studies were conducted with portable chambers placed over native species in the field with SO₂ and SO₂ + NO₂. Pollutant concentrations were measured and controlled with instruments located in a mobile laboratory. Each fumigation was of two hours duration and the concentration ranged from 0.5 to 11 ppm SO₂ and from 0.1 to 5 ppm NO₂. Concentrations of SO₂ above 2 ppm were required to cause injury to all but a few of the 87 species studied. Many of the native desert species proved to be highly resistant to injury from these gases.     

Seasonal variability of aerosol optical properties over Beijing

The knowledge of aerosol properties at local and regional scale is important in understanding of the global climate change. In this study, the aerosol optical properties over Beijing have been presented from the Aerosol Robotic Network (AERONET) measurements during 2002–2007. The aerosol optical depth (AOD) showed a distinct seasonal variation with high values in spring (March–May) and summer (June–August). The magnitude of Ångström exponent (α) was found to be relatively high throughout the year and the highest values (1.27) occurred in summer and the lowest (1.0) in spring. The water vapor retrieved from AERONET was found to be highest (2.60 cm) in summer. The fine modes of aerosol volume size distributions showed the highest peak around radius 0.15 μm in spring, autumn (September–November) and winter (December–February), and radius 0.19 μm in summer. The coarse modes showed the maxima peak at radius 3.0 μm in all seasons. The asymmetry factor (g) has considered as 0.65 at 440, 675, 870 and 1020 nm over Beijing in climate and radiation models. The average values of the single scattering albedo (SSA) at the four wavelengths were taken as 0.89, 0.91, 0.87 and 0.86 in spring, summer, autumn and winter, respectively. Both real and imaginary parts of the refractive index showed low wavelength dependence. The highest averages of real (1.52) and imaginary parts (0.0165) were found in spring and winter respectively in the wavelength range of 440–1020 nm. The aerosol properties over Beijing were found to highly dependent on season, and changes in aerosol properties were mainly attributed to the presence of dust as the main component during the spring season and the dominance of anthropogenic pollutants during the winter season.     

中国SO_2排放对日本SO_2浓度及硫沉降的影响

利用相关文献及来自酸沉降网的中、日两国各观测站点的SO2监测资料,分析了近十年来中国SO2的污染现状、趋势及排放量对下风向日本各观测站点SO2浓度及硫沉降量的影响。结果表明,通过文献分析可知,2001—2009中国的SO2年均质量浓度分布在40~50μg/m3,总体呈下降趋势;中国部分城市的SO2年均浓度与中国SO2排放量的相关性总体高于日本各观测站点的SO2年均浓度与中国SO2排放量的相关性,中国的SO2排放对日本各观测站点的SO2年均浓度影响总体较小;情景模拟分析发现,中国SO2排放量对日本各观测站点SO2年均浓度的贡献率在7.5%~44.0%,平均贡献率为22.6%;中国SO2排放量对日本各观测站点硫沉降的贡献率在8%~41%,平均贡献率为22.1%。     

NO2 and SO2 dispersion modeling and relative roles of emission sources over Map Ta Phut industrial area, Thailand

Map Ta Phut industrial area (MA) is the largest industrial complex in Thailand. There has been concern about many air pollutants over this area. Air quality management for the area is known to be difficult, due to lack of understanding of how emissions from different sources or sectors (e.g., industrial, power plant, transportation, and residential) contribute to air quality degradation in the area. In this study, a dispersion study of NO2 and SO2 was conducted using the AERMOD model. The area-specific emission inventories of NOx and SO2 were prepared, including both stack and nonstack sources, and divided into 11 emission groups. Annual simulations were performed for the year 2006. Modeled concentrations were evaluated with observations. Underestimation of both pollutants was Jbund, and stack emission estimates were scaled to improve the modeled results before quantifying relative roles of individual emission groups to ambient concentration overfour selected impacted areas (two are residential and the others are highly industrialized). Two concentration measures (i.e., annual average area-wide concentration or AC, and area-wide robust highest concentration or AR) were used to aggregately represent mean and high-end concentrations Jbfor each individual area, respectively. For AC-NO2, on-road mobile emissions were found to be the largest contributor in the two residential areas (36-38% of total AC-NO2), while petrochemical-industry emissions play the most important role in the two industrialized areas (34-51%). For AR-NO2, biomass burning has the most influence in all impacted areas (>90%) exceptJor one residential area where on-road mobile is the largest (75%). For AC-SO2, the petrochemical industry contributes most in all impacted areas (38-56%). For AR-SO2, the results vary. Since the petrochemical industry was often identified as the major contributor despite not being the largest emitter, air quality workers should pay special attention to this emission group when managing air quality for the MA.