Aqueous Phase Oxidation Of SO2 Research Articles

A light - Driven acidic positive feedback mechanism of sulfate formation

As the main source of atmospheric sulfate aerosol, the aqueous-phase oxidation of SO2 has been of great concern. Traditionally, the aqueous-phase oxidation of SO2 is considered a consumption process of atmospheric oxidation capacity; however, we report here that •OH radicals and other reactive oxygen species (ROS) can be generated in the photochemical reactions of bulk HSO3− solution. This •OH production pathway results in the fast sulfate formation in the photooxidation of dissolved SO2. The photochemical process is determined to be pH-dependent in which sulfate formation is promoted by decreasing pH. Hence, a light - driven acidic positive feedback mechanism is proposed that the oxidation of dissolved SO2 and the formation of •OH radicals have a synergistic promoting effect. These results indicate that the photochemistry of dissolved SO2 could be a missing source of aqueous •OH radicals as well as sulfate at regional to global scales.

Chemical composition, sources and evolution of wintertime inorganic and organic aerosols in urban Shanghai, China

China experienced severe haze pollution in the past decades. However, systematic characterization of atmospheric fine particles with advanced measurement techniques has been very scarce in Shanghai, which is the largest megacity in China. Herein, we present the characterization of non-refractory submicron aerosol (NR-PM1) in urban Shanghai during winter 2017 by applying an Aerosol Chemical Speciation Monitor (ACSM, Aerodyne Research Inc.). The NR-PM1 is predominated by organics (43%), followed by nitrate (29%), sulfate (18%), ammonium (7%), and chloride (3%). Regarding the organic aerosol (OA) factors, three organic aerosol factors were identified and classified as hydrocarbon-like organic aerosol (HOA), less-oxygenated organic aerosol (LO-OOA), and more-oxygenated organic aerosol (MO-OOA), which contributed 32%, 22%, and 46% to total organic aerosol respectively. The NR-PM1 composition exhibited an increase in secondary inorganic aerosol (SIA) (sulfate, nitrate and ammonium) contribution from clean episodes (49%) to pollution episodes (59%), while organic aerosol contribution decreased accordingly from 48% to 39%. The strong increase of sulfate in high-relative humidity (RH) pollution episodes indicated that aqueous-phase oxidation of SO2 could be an important formation process for sulfate during particulate air pollution period. The contribution of nitrate was elevated from 25% during clean episodes to 32% during polluted episodes, likely owing to the increase of relative humidity which facilitates the hydrolysis of N2O5 and the gas-to-particle partitioning of hydrophilic NH4NO3 and. Further analysis of atmospheric formation relevance suggested that less-oxygenated organic aerosol formation was mainly driven by aqueous-phase chemistry reactions, whereas photochemical oxidation became an important process for more-oxygenated organic aerosol formation. Meanwhile, less-oxygenated organic aerosol formation may also be influenced by atmospheric oxidative tracer (i.e., Ox), as less-oxygenated organic aerosol exhibited a distinct peak at noon under high-relative humidity condition.

Impacts of the COVID-19 lockdown on atmospheric oxidizing capacity and secondary aerosol formation over the Beijing-Tianjin-Hebei region in Winter-Spring 2020

By using WRF-Chem coupled with a heterogeneous reaction mechanism for sulfate formation, this study investigated the impact of meteorological condition and emission changes on chemical species, atmospheric oxidizing capacity (AOC), and secondary aerosol formation during the COVID-19 lockdown period from 23 January to April 8, 2020, focusing on a severe haze event on 7–14 February. The model with the new sulfate formation scheme reasonably reproduces the spatial-temporal distribution of meteorological variables and chemical species, and significantly improves predictions for both sulfate and SO2 concentrations, as well as for PM2.5, ammonium, and nitrate to some extent. It is found that the adverse meteorological conditions were the main cause for the haze event formation, whereas emission reduction due to the lockdown somewhat decreased PM2.5 concentration on average in the Beijing-Tianjin-Hebei (BTH) region. Compared with the same period in 2019, increased surface air temperature and relative humidity (RH) and decreased planetary boundary layer height (PBLH) facilitated accumulation of pollutants and formation of secondary aerosols during the haze episode in 2020, whereas the emission reduction due to the lockdown led to decreases in SO2, NO2, primary PM2.5 (PPM2.5), black carbon (BC), primary organic aerosols (POA), nitrate and ammonium concentrations, but increases in O3, sulfate and secondary organic aerosol (SOA) concentrations, due to the combined effect of changes in emissions and AOC. Gas and aqueous phase oxidation of SO2 accounted for approximately 24% of sulfate formation, while the heterogeneous reaction of Mn-catalytic oxidation of SO2 on aerosol surfaces dominated sulfate formation (76%) during the haze episode in the BTH region. Both adverse meteorological conditions and emission reductions increased heterogeneous sulfate formation rate mainly through altering aerosol surface area (ASA), pH, and Mn2+ concentration. Chemical species varied diversely during the three subperiods before (Period-1, 15–22 January) and during the lockdown (Period-2, 23 January to 5 March and Period-3, 6 March to 8 April) over the BTH. NO2 concentration firstly decreased and then rebounded, whereas O3 concentration increased gradually from the Period-1 to Period-3. All aerosols except SOA decreased throughout the lockdown period, whereas SOA peaked in the Period-2 due to its strong sensitivity to increasing AOC. Sulfate concentration decreased from the Period-1 to Period-2, mainly due to more adverse meteorological conditions in the Period-1, although sulfate increased slightly due to increasing AOC in the Period-2. The large difference in the direction and magnitude of species variations during the COVID-19 lockdown indicates the complex interplay among meteorology, emission, and chemistry.

Recommendations for HCHO and SO2 Retrieval Settings from MAX-DOAS Observations under Different Meteorological Conditions

Recently, the occurrence of fog and haze over China has increased. The retrieval of trace gases from the multi-axis differential optical absorption spectroscopy (MAX-DOAS) is challenging under these conditions. In this study, various reported retrieval settings for formaldehyde (HCHO) and sulfur dioxide (SO2) are compared to evaluate the performance of these settings under different meteorological conditions (clear day, haze, and fog). The dataset from 1st December 2019 to 31st March 2020 over Nanjing, China, is used in this study. The results indicated that for HCHO, the optimal settings were in the 324.5–359 nm wavelength window with a polynomial order of five. At these settings, the fitting and root mean squared (RMS) errors for column density were considerably improved for haze and fog conditions, and the differential slant column densities (DSCDs) showed more accurate values compared to the DSCDs between 336.5 and 359 nm. For SO2, the optimal settings for retrieval were found to be at 307–328 nm with a polynomial order of five. Here, root mean square (RMS) and fitting errors were significantly lower under all conditions. The observed HCHO and SO2 vertical column densities were significantly lower on fog days compared to clear days, reflecting a decreased chemical production of HCHO and aqueous phase oxidation of SO2 in fog droplets.

Size-segregated aerosols over a high altitude Himalayan and a tropical urban metropolis in Eastern India: Chemical characterization, light absorption, role of meteorology and long range transport

A study has been conducted focusing on the chemical and optical characterization of water soluble inorganic and organic components of aerosols at different sizes, over a high altitude Himalayan station, Darjeeling (27.1° N and 88.15° E, 2200 m amsl) and a tropical urban metropolis, Kolkata (22.5° N, 88.3° E, ~6 m amsl) for two-year long period (March 2016–February 2018). It was observed that local meteorology and long range transport of pollution plumes have played the pivotal role in governing the temporal variation of the mass distribution and concentration of aerosols and its various components over both the sites. The aerosol mass-size distributions were found to be bimodal in nature with the relative dominance of accumulation mode (0.1–1.0 μm) over coarse mode (1.8–10 μm) over both the stations, indicating dominance of the anthropogenic emissions. Among the size classes, accumulation mode aerosols alone contributed 55–75% over Darjeeling and 40–60% over Kolkata to PM10. The coarse mode aerosols were mainly consisted of primary inorganic species over Kolkata and water soluble organic carbons (WSOC) over Darjeeling whereas the fine mode aerosols (accumulation: 0.1–1.0 μm) were primarily composed of the secondary inorganic aerosols for both the stations. Irrespective of the seasons and stations, SO42− and NH4+ exhibited peaks in the mass-size distribution at 1.0–0.1 μm whereas that of NO3− varied with the seasons. The photochemical oxidation and the aqueous phase oxidation of SO2 (g) were the pathways for SO42− formation over Darjeeling whereas the later dominated over Kolkata. Concentration weighted trajectory (CWT) model has revealed that the secondary inorganic aerosols and WSOC were local/regional in origin over Kolkata megacity whereas Darjeeling was influenced by mixed sources. The accumulation mode aerosols were found to be the highest light absorbing over both the stations irrespective of the seasons. Over Darjeeling, the absorption coefficient (babs_365) and the mass absorption efficiency (MAE) of WSOC were maximum for local biomass burning aerosols than the transported plumes whereas those over Kolkata were maximum for transported biomass burning plumes from Eastern Ghats.

Changes in ammonia and its effects on PM2.5 chemical property in three winter seasons in Beijing, China

NH3, SO2, NOx and the inorganic ions of PM2.5 in winter 2009, 2014 and 2016 were examined to investigate the change in NH3 and aerosol chemistry in Beijing, China. NH3 concentrations showed an increase by 59% on average, in contrast to the decrease of SO2 by 63% from winter 2009 to 2016. The mean mass ratio of NH3/NHx was 0.83 ± 0.12 in 2016, which is higher than those obtained in 2009 and 2014, implying more NHx remaining as free NH3 in 2016 winter. Our findings suggest that vehicles exhaust emissions are an important NH3 source in urban central atmosphere of Beijing in winter. Despite the observed NOx presenting declining trends from 2014 to 2016, nitrate concentrations even exhibited a significant increasing trend, which may be largely attributable to high NH3 levels. An in-depth analysis of measured NH3 and aerosol species in a heavy pollution episode in December 2016, combined with the acidity predicted by ISORROPIA II model demonstrated abundant NH3 most of the time in air, where NH3 is not only a precursor for NH4+ but also effect the neutralization of SO42− and NO3− in PM2.5. With high RH and low photochemical activity, elevated NO3− concentration was attributed to an enhanced heterogeneous conversion of NOx to HNO3 to form NH4NO3 in pollution transport stage. The decrease in NOx from high level and the increase in NH3, with peaks of SO42− occurring were observed in pollution cumulative stage. The aqueous-phase oxidation of SO2 by NO2 to sulfate might play an important role with high pH values. Our results suggested that the simultaneous control of NH3 emissions in conjunction with SO2 and NOx emissions would be more effective in reducing particulate matter PM2.5 formation.

Impacts of relative humidity on fine aerosol properties via environmental wind tunnel experiments

This study used a closed-circuit boundary-layer wind tunnel, with a series of instruments including SO2, NO2, O3, NH3, and PM2.5 monitors and an Aerodyne Aerosol Mass Spectrometer (AMS), to explore the effects of relative humidity (RH) on properties of ambient fine particles (PM2.5 and PM1) in the northern suburbs of Nanjing. The results showed under all conditions the PM1 concentration were influenced largely by organic matter, and meanwhile, the contribution of sulfate decreased. Under non-humidification conditions, the mass concentrations of fine particles increased with the increase of RH. The mass concentration of PM2.5 was not influenced by the SO2 concentration and changed in a manner similar to those of the NO2 and NH3 concentrations at higher RH; however, the mass concentration varied inversely with changes of O3 concentration. The mass concentration and mass fraction of sulfate and nitrate changed in different manners as RH varied. CxHy+ ions took up the highest percentage of organic matter in the AMS spectra, indicating organics in a large part might be emitted as primary organic aerosol (POA), and the fine particles were overall alkaline. With atomized humidification (at constant temperature), the mass concentrations of all fine particles showed an explosive increase, with PM2.5 levels rising at an average rate of 11.9 μg/m3·min. The increase in the fine particle concentration was primarily due to increases in the PM1-2.5 level. The percentage of organic matter increased with RH, with CxHyO+ and CxHyOz+ ions becoming the major ion groups indicating the dominance of secondary organic aerosol (SOA) species, facilitated by high humidity. The SO42−/SO2 ratio increased with RH, indicating that sulfate was formed at high humidity rapidly via an aqueous-phase oxidation of SO2 and results show that O3 might become an important oxidant. The fine particles were acidic, and the increased O/C ratio also indicates the SOA contribution.

Nighttime particle growth observed during spring in New Delhi: Evidences for the aqueous phase oxidation of SO2

Aerosol size distributions were measured using a scanning mobility particle sizer (SMPS), and also PM1 (particulate matter ≤ 1 μm in aerodynamic diameter) samples were collected in parallel at a representative site in New Delhi during spring in 2013 and 2014. Based on the temporal variation of particle count mean diameter (CMD), sampling periods are characterized as growth events and non-growth events. Particle size distribution measurements suggest that some consecutive nights experienced unique nighttime subsequent growth of particles, which sustained for a longer period. Average particle growth rate measured during growth events was 5.64 ± 3.03 nm h−1. Atmospheric trace gas concentrations and meteorological data show that these growth events (nighttime) are influenced by higher concentrations of gases, e.g., NO2 (56.5 ± 29.7 μg m−3), SO2 (9.34 ± 1.14 μg m−3) and RH (45.7 ± 9.5%) than those of non-growth events (daytime) (37.9 ± 18.6 μg m−3, 7.19 ± 2.08 μg m−3 and 37.7 ± 6.9%, respectively). Further, analysis of PM1 samples collected during the study period shows that the particulate water-soluble organic carbon (WSOC) (12.7 ± 4.1 μg m−3), NH4+ (9.4 ± 3.2 μg m−3), SO42− (2.03 ± 0.70 μg m−3), K+(1.06 ± 0.40 μg m−3), and NO2− + NO3− (0.59 ± 0.36 μg m−3) are the major contributors of particulate mass, wherein NH4+, SO42−, K+, NO2− + NO3− mass concentrations were higher during growth events. Correlation study shows that nighttime aerosol composition during growth (in sub-micron range) events are more enriched by inorganic species (i.e., NH4NO3, (NH4)2SO4 and H2SO4 vapors) as compared to organics (i.e., WSOC, does not show much difference in growth events and non events). Our results suggest that nighttime sulfate formation at the site is mostly mediated by high NO2 and NH3 at elevated RH. For the formation of sulfate and other inorganic species, a nighttime atmospheric chemistry is proposed, which is linked to particle growth. Growth events observed typically in nighttime have both biomass burning and anthropogenic influences as indicated by high concentrations of WSOC, K+ and black carbon in PM1 and carbon monoxide in gas phase.

Trends in heterogeneous aqueous reaction in continuous haze episodes in suburban Shanghai: An in-depth case study

Heterogeneous aqueous reaction plays important roles in the enhanced formation of secondary aerosols during haze. However, its occurrence in haze episodes remains poorly understood. In this study, the trends in heterogeneous aqueous reaction in continuous haze episodes were investigated by an in-depth case analysis. The highly time-resolved measurements of water-soluble inorganic ions of PM2.5 were conducted in a suburban of Shanghai, China, and continuous haze episodes, which occurred from Feb. 18 to Feb. 28, were selected as studied cases. Results showed that fine particle pollution in Baoshan was serious. High concentrations of secondary inorganic aerosol ions and the higher sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) on haze days indicated enhanced conversions from SO2 and NOx to their corresponding particulate phases. The high-nitrate haze episode and the high-sulfate haze episode were identified. Further simulations revealed that the PM2.5 particles had strong acidity during the high-nitrate and high-sulfate haze episodes whether they were calculated by E-AIM 4 or by ISORROPIA II. It was found that particulate liquid water was more sensitive to nitrate than sulfate, and played significant roles in the heterogeneous aqueous reactions of NO2 and secondary nitrate formation during haze episodes, especially in the high-sulfate haze episode. Further analysis indicated that the high-nitrate haze episode favoured the occurrence of heterogeneous aqueous phase oxidation of SO2, and the more water was in the particles, the more SO2 was converted to sulfate aerosols. This work provides an important field measurement-based evidence for understanding the important contributions of the heterogeneous aqueous reactions to secondary aerosol pollution and the tendencies of heterogeneous aqueous reactions in the formation of secondary sulfate and nitrate aerosols in suburban Shanghai.

Secondary inorganic aerosols formation during haze episodes at an urban site in Beijing, China

Severe PM2.5 pollution was observed frequently in Beijing. We conducted highly time-resolved measurements of inorganic ions associated with PM2.5 at an urban site in Beijing from 10 February to 19 March, 2015. The average PM2.5 mass concentrations during the six haze episodes ranged from 113.0 μg/m3 to 182.6 μg/m3, which were more than 8 times higher than those observed in clean periods. The secondary inorganic species (NH4+, SO42− and NO3−) in PM2.5 sharply increased during the haze episodes, indicating more extensive formation of SO42− and NO3−. The sulfur oxidation ratios (SOR) and the nitrogen oxidation ratios (NOR) in haze episodes were higher than those in clean periods, which indicated that secondary transformation in haze episodes was more significant than those in clean periods. No correlations between SOR and the oxidants (O3 and HONO) and the temperature were found, whereas a high correlation between SOR and relative humidity (RH) was found in haze episodes, which implied that sulfate was mainly produced by the aqueous-phase oxidation of SO2 rather than the gas-phase conversion of SO2 to sulfate. The conversion of SO2 to SO42− was observed to be sensitive to changes in RH. Furthermore, the SOR sharply increased at RH > 60% with the highest value of 0.88 at RH around 80% during complicated pollution. NO2 played an important role in the rapid sulfate formation with high RH and NH3 neutralization conditions in haze episodes in Beijing. The impact of RH was less apparent for nitrate than for sulfate. Nitrate was found to be produced mainly by photochemical and heterogeneous reactions, while heterogeneous reactions had a greater influence on NOR at nighttime. The NO3−/SO42− ratio indicated that mobile sources contributed more to the formation of PM2.5 than stationary sources. The result suggested the need for control of vehicle emissions to reduce the high levels of NOx and nitrate and the severe PM2.5 pollution in Beijing.

Changes in inorganic fine particulate matter sensitivities to precursors due to large-scale US emissions reductions.

We examined the impact of large US emissions changes, similar to those estimated to have occurred between 2005 and 2012 (high and low emissions cases, respectively), on inorganic PM2.5 sensitivities to further NOx, SO2, and NH3 emissions reductions using the chemical transport model GEOS-Chem. Sensitivities to SO2 emissions are larger year-round and across the US in the low emissions case than the high emissions case due to more aqueous-phase SO2 oxidation. Sensitivities to winter NOx emissions are larger in the low emissions case, more than 2× those of the high emissions case in parts of the northern Midwest. Sensitivities to NH3 emissions are smaller (∼40%) in the low emissions case, year-round, and across the US. Differences in NOx and NH3 sensitivities indicate an altered atmospheric acidity. Larger sensitivities to SO2 and NOx in the low emissions case imply that reducing these emissions may improve air quality more now than they would have in 2005; conversely, NH3 reductions may not improve air quality as much as previously assumed.

Secondary Formation of Sulfate and Nitrate during a Haze Episode in Megacity Beijing, China

A heavy haze episode that occurred in Beijing from 20 September to 27 September, 2011 was observed to explore the secondary processes of the haze episode. During the haze episode, the relatively stable synoptic conditions and regional transport from polluted areas in the south and southwest of Beijing favored the formation of haze. Significant increases of PM2.5/PM10 ratio was observed during haze period, which implied that the haze was caused by fine particles. Additionally, the presence of secondary inorganic pollutants (SO42–, NO3– and NH4+) sharply increased during the haze episode, which indicated that secondary processes significantly strengthened the haze episode. The sulfur oxidation ratio (SOR) sharply increased from a non-haze episode with a highest value of 0.11 to a haze episode with a highest value of 0.62. Low correlations between SOR and O3 and the temperature were found, whereas a high correlation between SOR and RH was found during the haze episode, which implied that sulfate was mainly produced by the aqueous-phase oxidation of SO2 rather than the gas-phase conversion of SO2 to sulfate in haze episode in Beijing. Furthermore, a fine linear relationship between SOR and the surface area (dS) of particles smaller than 1 µm confirmed the heterogeneous processes of sulfate formation in haze episode. The nitrogen oxidation ratio (NOR) also sharply increased from a non-haze episode with a highest value of 0.03 to a haze episode with a highest value of 0.26, which indicated more intense secondary formation of nitrate in haze episode. Nitrate was found to be mainly produced by a homogenous reaction under ammonium-rich conditions. Higher RH in haze episode reduced the thermodynamic equilibrium constant Ke’, and favored the thermodynamic equilibrium reaction of HNO3(g) + NH3(g) ↔ NH4NO3(s, aq) to formed nitrate, which might help explain the enhanced homogenous production of nitrate in haze episode. In addition, a good empirical fit (R2 = 0.70) between NOR and dS was found, which indicated that the particle surface area significantly contributed to the intense homogeneous production of nitrate in haze episode.

SO2 oxidation and nucleation studies at near-atmospheric conditions in outdoor smog chamber

Environmental context Nucleation, a fundamental step in atmospheric new-particle formation, is a significant source of atmospheric aerosols. Most laboratory experiments investigate H2SO4 nucleation based on indoor chambers or flow tube reactors, and find discrepancies with field observations. Here a large outdoor smog chamber is used to study the relationship between SO2 and nucleation rates, and demonstrate the importance of aqueous phase oxidation of SO2 by H2O2 and other oxidants. Abstract Particle formation under different initial ambient background conditions was simulated in a dual outdoor smog chamber for the SO2 and O3–SO2 systems with and without sunlight, as well as a propylene–NOx–SO2–sunlight system. An exponential power of 1.37 between nucleation rates at 1nm (J1) and SO2 gas phase concentrations was obtained for the SO2–sunlight system and a minimum of 0.45ppbSO2 is required by this relationship to initiate nucleation (J1 is equal to 1cm–3s–1). An investigation of the O3–SO2–sunlight/dark system showed that the presence of O3 contributed to the particle nucleation and growth at night; however, it only enhanced the particle growth in the daytime when H2SO4 photochemistry was present. In the presence of an OH• scavenger, the O3–SO2 system did not show particle nucleation, suggesting that the scavenger cut off this pathway of SO2 oxidation. A lower nucleation rate and higher particle grow rate were also observed for SO2 oxidation in the presence of propylene and NOx. However a higher SO2 decay rate was obtained for the propylene system especially under high relative humidity, which was not observed in the O3–SO2 system. This suggests that aqueous phase oxidation of SO2 from H2O2, RO2• and other oxidants produced in the propylene–NOx system contribute to the particle growth.

Evaluation of several PM2.5 forecast models using data collected during the ICARTT/NEAQS 2004 field study

Real‐time forecasts of PM2.5 aerosol mass from seven air quality forecast models (AQFMs) are statistically evaluated against observations collected in the northeastern United States and southeastern Canada from two surface networks and aircraft data during the summer of 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)/New England Air Quality Study (NEAQS) field campaign. The AIRNOW surface network is used to evaluate PM2.5 aerosol mass, the U.S. EPA STN network is used for PM2.5 aerosol composition comparisons, and aerosol size distribution and composition measured from the NOAA P‐3 aircraft are also compared. Statistics based on midday 8‐hour averages, as well as 24‐hour averages are evaluated against the AIRNOW surface network. When the 8‐hour average PM2.5 statistics are compared against equivalent ozone statistics for each model, the analysis shows that PM2.5 forecasts possess nearly equivalent correlation, less bias, and better skill relative to the corresponding ozone forecasts. An analysis of the diurnal variability shows that most models do not reproduce the observed diurnal cycle at urban and suburban monitor locations, particularly during the nighttime to early morning transition. While observations show median rural PM2.5 levels similar to urban and suburban values, the models display noticeably smaller rural/urban PM2.5 ratios. The ensemble PM2.5 forecast, created by combining six separate forecasts with equal weighting, is also evaluated and shown to yield the best possible forecast in terms of the statistical measures considered. The comparisons of PM2.5 composition with NOAA P‐3 aircraft data reveals two important features: (1) The organic component of PM2.5 is significantly underpredicted by all the AQFMs and (2) those models that include aqueous phase oxidation of SO2 to sulfate in clouds overpredict sulfate levels while those AQFMs that do not include this transformation mechanism underpredict sulfate. Errors in PM2.5 ammonium levels tend to correlate directly with errors in sulfate. Comparisons of PM2.5 composition with the U.S. EPA STN network for three of the AQFMs show that sulfate biases are consistently lower at the surface than aloft. Recommendations for further research and analysis to help improve PM2.5 forecasts are also provided.

A global model of the coupled sulfur/oxidant chemistry in the troposphere: The sulfur cycle

A sulfur cycle chemistry scheme with dimethyl sulfide (DMS), SO2, sulfate, H2S, and methanesulfonic acid (MSA) is included in the OsloCTM2 model, and concentrations of sulfur are calculated interactively with the oxidant chemistry. This allows more consistent estimates of aqueous phase oxidation of SO2 to sulfate by O3, H2O2, and HO2NO2. The year 1996 is chosen as the standard, and a model run with 1996 meteorology and emissions is compared with 1996 observations. The results agree well with observations overall, although the model tends to overestimate SO2 and underestimate sulfate in Northern Hemisphere winter owing to an oxidation limitation. A global budget for 1996 quantifying the various processes is investigated. Our model results give a global lifetime (global burden) of 1 day (0.25 Tg(S)) and 3.8 days (0.5 3 Tg(S)) for SO2 and sulfate. Differences between the Southern Hemisphere, characterized by natural emissions and by loss of SO2 by O3 and H2O2 oxidation, and the Northern Hemisphere, characterized by anthropogenic emissions and by large loss by dry deposition, are revealed. Significant changes in sulfur emissions have occurred over the last decades with decrease in the Unites States and Europe and increase in Southeast Asia. U.S., European, and Chinese SO2 emissions have changed by −17.6%, −47.5%, and +93%, respectively. To study the impact of emission changes on the atmospheric composition, we have calculated distributions using the Global Emissions Inventory Activity (GEIA) 1985 inventory. The changes in sulfur emissions have significant changes on the sulfur concentrations and also some effect upon the oxidants. Increased emissions of NOx and hydrocarbons in China enhance O3, but increased sulfur inhibit the increase. The SO2 oxidation by OH, which can lead to formation of new sulfate particles, is given special attention. The model run using GEIA 1985 anthropogenic emission inventory is compared with other model studies.

Analysis of regional budgets of sulfur species modeled for the COSAM exercise

The COSAM intercomparison exercise (comparison of large-scale sulfur models) was organized to compare and evaluate the performance of global sulfur cycle models. Eleven models participated, and from these models the simulated surface concentrations, vertical profiles and budget terms were submitted. This study focuses on simulated budget terms for the sources and sinks of SO2 and sulfate in three polluted regions in the Northern Hemisphere, i.e., eastern North America, Europe, and Southeast Asia. Qualitatively, features of the sulfur cycle are modeled quite consistently between models, such as the relative importance of dry deposition as a removal mechanism for SO2, the importance of aqueous phase oxidation over gas phase oxidation for SO2, and the importance of wet over dry deposition for removal of sulfate aerosol. Quantitatively, however, models may show large differences, especially for cloud-related processes, i.e., aqueous phase oxidation of SO2 and sulfate wet deposition. In some cases a specific behavior can be related to the treatment of oxidants for aqueous phase SO2 oxidation, or the vertical resolution applied in models. Generally, however, the differences between models appear to be related to simulated cloud (micro-)physics and distributions, whereas differences in vertical transport efficiencies related to convection play an additional rôle. The estimated sulfur column burdens, lifetimes and export budgets vary between models by about a factor of 2 or 3. It can be expected that uncertainties in related effects which are derived from global sulfur model calculations, such as direct and indirect climate forcing estimates by sulfate aerosol, are at least of similar magnitude.

Terrestrial sources and distribution of atmospheric sulphur

The general circulation model ECHAM has been coupled to a chemistry and sulphur cycle model to study the impact of terrestrial, i.e. mostly anthropogenic sulphur dioxide (SO2), sources on global distributions of sulphur species in the atmosphere. We briefly address currently available source inventories. It appears that global estimates of natural emissions are associated with uncertainties up to a factor of 2, while anthropogenic emissions have uncertainty ranges of about +/− 30 per cent. Further, some recent improvements in the model descriptions of multiphase chemistry and deposition processes are presented. Dry deposition is modelled consistently with meteorological processes and surface properties. The results indicate that surface removal of SO2is less efficient than previously assumed, and that the SO2lifetime is thus longer. Coupling of the photochemistry and sulphur chemistry schemes in the model improves the treatment of multiphase processes such as oxidant (hydrogen peroxide) supply in aqueous phase SO2oxidation. The results suggest that SO2oxidation by ozone (O3) in the aqueous phase is more important than indicated in earlier work. However, it appears that we still overestimate atmospheric SO2concentrations near the surface in the relatively polluted Northern Hemisphere. On the other hand, we somewhat underestimate sulphate levels in these regions, which suggests that additional heterogeneous reaction mechanisms, e.g. on aerosols, enhance SO2oxidation.

A multielement tracer technique for the determination of SO2 oxidation in clouds

A technique was developed in this laboratory which uses similarities in the physical and chemical properties of SO4 and Se aerosols to quantitatively resolve SO4 in cloud water derived from the gas and aqueous phase oxidation of SO2. We report here the extension of the technique to include As and Sb as tracers and present experimental data to verify assumptions in our earlier studies regarding the sampling of precloud aerosols. In situ SO4 production in clouds [(SO4in)] is given by [SO4in] = [(SO4/M) cw ‐ α/(β,δ,τ) (SO4/M)aa] (M)cw where M represents Se, As, or Sb; α,β, δ and τ are the scavenging efficiencies of SO4, Se, As, and Sb aerosols, respectively; and cw and aa represent cloud water and ambient precloud aerosols. Field data from three cloud systems are presented, which show that δ/β = 0.92 ± 0.12 and τ/β; = 0.95 ± 0.13. Therefore within experimental uncertainties, the scavenging efficiencies of As and Sb are determined to be equal to that of Se. Results of in‐cloud oxidation determined in three clouds using Se, As, and Sb are in excellent agreement. Regression analysis of SO4in by As and Se had a slope of 1.02 ± 0.05 (r=0.85). Similarly for Sb and Se the slope was 1.06 ± 0.05 (r=0.85).

Sulfate over the North Atlantic and adjacent continental regions: Evaluation for October and November 1986 using a three‐dimensonal model driven by observation‐derived meteorology

A high‐resolution three‐dimensional Eulerian transport and transformation model has been developed to simulate concentrations of tropospheric sulfate for specific times and locations; it was applied over the North Atlantic and adjacent continental regions during October and November 1986. The model represents emissions of anthropogenic SO2 and sulfate and of biogenic sulfur species, horizontal and vertical transport, gas phase oxidation of SO2 and dimethylsulfide, aqueous phase oxidation of SO2, and wet and dry deposition of SO2, sulfate, and methanesulfonic acid (MSA). The meteorological driver is the 6‐hour output from the forecast model of the European Centre for Medium‐Range Weather Forecasts. Calculated sulfate concentrations and column burdens, examined in detail for specific dates, are related to existing weather patterns. These quantities exhibit rich temporal and spatial structure; the characteristic (1/e) autocorrelation time for the sulfate column burdens over the central North Atlantic averages 10 hours; 95% of the values are 25 hours or less. The characteristic distance of spatial autocorrelation over this region depends on direction; the minimum value of the average is 900 km and the minimum values for the 10th and 90th percentiles are 400 and 1700 km. Daily average model sulfate concentrations at the lowest vertical level accurately represent the spatial variability, episodicity, and absolute magnitudes of surface concentrations measured by monitoring stations in Europe, Canada, New York state, and Barbados; over 50% of model concentrations are within a factor of 3 of the observations. Over 50% of weekly model sulfate wet deposition amounts are within a factor of 3 of observations from U.S. monitoring stations. Over the 34‐day period modeled, contributions from anthropogenic emissions to the sulfate over the mid North Atlantic Ocean ranged from 44 to 66%, contributions from biogenic emissions were between 6 and 12%. Calculated average yields for sulfate (47 to 72%) and MSA (13%), and turnover times for SO2 (2 to 3 days) and sulfate and MSA (4 to 8 days) are comparable to previous estimates; however, these quantities depend on meteorological conditions and on the geographical and vertical distributions of the material.

A three‐dimensional numerical model of cloud dynamics, microphysics, and chemistry: 4. Cloud chemistry and precipitation chemistry

A study of the cloud chemistry and precipitation chemistry of the three‐dimensional cloud chemical modeling of a severe local storm case (Wang and Chang, this issue) is discussed in this paper. In our simulation the microphysical processes, especially those related to the ice phase, were found to have significant effects on influencing both the rhythm of time evolution and the amount of quantitative variation of pollutants. Most chemical species in the ice phase particles were transformed from liquid phase droplets by the riming process. The ratio of the transfer of chemical species from aqueous phase to ice phase induced by riming to that induced by freezing was about 55 to 1 for N(V) and 8 to 1 for S(VI). The average equivalent pH value had a linear correlation with the logarithm of total water content and with the logarithm of [S(VI)] + [N(V)] in the cloud. The average equivalent pH value for the whole cloud changed from 5.1 at 28 min to 4.4 at 55 min. Most low pH values appeared in the less convective region. For this particular case study, aerosol scavenging was the major source of S(VI) production, which provided a total amount 50 times that provided by sulfur oxidation in the cloud. The major contributor of sulfur oxidation changed during the lifetime of the modeled storm. The peaks of acid deposition did not correspond to the peaks of precipitation. The sub cloud dissolution and microphysics‐related transformation played an important role in the acid production and deposition. The nitric acid production total in the sub cloud area doubled that in the cloud. Most of the S(VI) produced by the aqueous phase SO2 oxidation was also found to be due to sub cloud processes.