The relationship of sulfur emissions to sulfate in precipitation—II. Gas phase processes

A climatological box model is applied to wet deposition of sulfur in eastern North America using the extreme assumption that all wet-deposited sulfates originate in sulfate aerosol. The measured sulfate in precipitation during 1977–1979 constrains the probability that an SO₂ molecule emitted in the eastern United States is oxidized before deposition or outflow from the region to values greater than 0.5 and more likely near 1.0. This result implies that uniform SO₂ emission reductions will produce nearly proportional reductions in wet sulfates originating in those emissions and deposited on land. A similar result was obtained previously using the more likely assumption that oxidation and removal of SO₂ in precipitating clouds is the major source of wet deposition of sulfur. Therefore, it is argued that uniform regional reductions in annual average SO₂ emissions will produce nearly proportional reductions in wet sulfur deposited on land and originating in those emissions. The amount of wet sulfate deposition is demonstrated to constrain the mean scale of transport along air parcel trajectories for the precursor of wet sulfur, whether SO₂ or sulfate aerosol, to values greater than 900 km. An examination of previous microscopic photochemical models indicates that the sulfate aerosol formation rate is roughly proportional to local SO₂ concentrations, an inference which is consistent with the result of the climatological model.     

Some results of snow chemical surveys in the Kunnes River valley,East Tienshan mountains,China

Chemical surveys of snow were carried out in the upper reaches of the Kunnes River, a tributary of the Yili River in East Tienshan Mountains, China. Some surprisingly high values of sodium and potassium (K⁺+Na⁺) ranging from 4.44 to 8.99 mg/l compared with other data from neighboring areas are detected. Moreover, some relative high values of SO₄²⁻ with mean concentration 15.8 mg/l for new snow and 14.40 mg/l for deposited snow, ranging from 10.43 to 23.71 mg/l are also found. Therefore, it is inferred that the sodium and potassium (K⁺+Na⁺) are in the forms of sulfate and that the sources of the sulfate are deserts and some dried lakes in Central Asia. It is also found that there is obviously spatial variation of ions such as K⁺+Na⁺, Ca²⁺, SO₄²⁻ and HCO₃⁻. The concentrations of K⁺+Na⁺ and SO₄²⁻, and that of Ca²⁺ and HCO₃⁻ have similar spatial pattern. The temporal pattern of ion concentration of new snow is considered to be mainly controlled by the depth and area of snow cover in the study area and in the areas to the west.     

Gaseous Sulfur Pollutants from Urban and Natural Sources

Major aspects of the circulation through the atmospheric environment of sulfur pollutants have been estimated, including source magnitudes, residual atmospheric concentrations, and scavenging processes. The compounds considered include SO₂ and H₂S, as well as sulfates. One-third of the sulfur reaching the atmosphere comes from pollutant sources, mainly as SO₂. Within the atmosphere there is a net transfer of sulfur from land to ocean areas. Pollutant sources annually amount to 73 × 10⁶ tons as sulfur while natural sources amount to 142 × 10⁶ tons, mainly as H₂S and sulfate sea spray. More than two thirds of the natural and pollutant sulfur emissions occur in the northern hemisphere. When only pollutant emissions are considered, 93 per cent occur in the northern hemisphere.     

Modeling of Sulfur Dioxide Emissions and Acidic Precipitation at Mesoscale Distances

A steady state mesoscale model developed to predict primary SO₂ concentrations from a single point source is presented. The model was validated with data from the Midwest Interstate Sulfur Transport and Transformation (MISTT) project, with root mean square errors of 9.69 μg m^?3 and 0.42 μg m^?3 for SO₂ and SO₄ respectively. Wet deposition (washout and rainout), eddy dispersivity, dry deposition of SO₂ and mean wind speed were found to be the most important factors controlling sulfur dioxide and sulfate concentrations. Estimation of precipitation acidity was then carried out using scavenging theory. The greatest potential acidification occurred approximately 200 km from the source along plume centerllne, which indicates a rather local effect as opposed to a long distance effect. The cross-plume influence was up to 60 km in width at a distance of 400 km from the source.     

Arctic air pollution: An overview of current knowledge

From December to April, the Arctic air mass is polluted by man-made mid-latitudinal emissions from fossil fuel combustion, smelting and industrial processes. In the rest of the year, pollution levels are much lower. This is the outcome of less efficient pollutant removal processes and better south (S) to north (N) transport during winter. In winter, the Arctic air mass covers much of Eurasia and N. America. Meteorological flow fields and the distribution of anthropogenic SO₂ emissions in the northern hemisphere favor northern Eurasia as the main source of visibility reducing haze. Observations of SO₄²⁻ concentrations in the atmosphere throughout the Arctic yield, depending on location and year, a January–April mean of 1.5–3.9 μg m⁻³ in the Norwegian Arctic to 1.2–2.2 μg m⁻³ in the N. American Arctic. An estimate of the mean vertical profile of fine particle aerosol mass during March and April shows that, on average, pollution is concentrated in the lower 5 km of the atmosphere. Not only are anthropogenic particles present in the Arctic atmosphere but also gases such as SO₂, perfluorocarbons and pesticides. The acidic nature and seasonal variation of Arctic pollution is reflected in precipitation, the snowpack and glacier snow in the Arctic. A pH of 4.9–5.2 in winter and ~ 5.6 in summer is expected in the absence of calcareous wind blown soil. Glacial records indicate that Arctic air pollution has undergone a marked increase since the mid 1950s paralleling a marked increase in SO₂ and NO_x emissions in Europe. Effects of Arctic pollution include a reduction in visibility and perturbation of the solar radiation budget in April–June. Potential effects are the acidification and toxification of sensitive ecosystems.     

Major inorganic ions in North Pole snow samples

Major inorganic ions, pH, total N and P were analyzed in eight arctic snow samples collected in March, April and May 1984 during an expedition in the North Pole region (N83₀18′ W73₀06′ - N89.960₀). The concentrations of the ions in different samples were close to each other and the values obtained seem to be representative for mean concentrations in the snow. In the sample taken from the North Pole the pH value was 5.00 while the H⁺-, SO^2?₄- and NO^?₃-concentrations were 0.24, 6.2 and 4.3 μmol/l, respectively. The concentrations are exceedingly low and agree very well with earlier results from arctic snow samples.     

The scavenging of atmospheric sulfate by arctic snow

Scavenging ratios for sulfate on the south-central Greenland Ice Sheet at Dye 3 have been computed for 1982–1984. The ratios are based on measured concentrations in snow and estimated concentrations in air. The snow data have been obtained from snowpit samples which were dated by comparing δ¹⁸O values with meteorological records. The airborne concentrations have been estimated from data collected at coastal Greenland sites. Scavenging ratios resulting from this process are found to be in the range ~ 100–200 in winter and ~ 200–400 in summer. The greater summer values are attributed to increased riming, resulting in scavenging of sulfate as condensation nuclei and possible oxidation of SO₂ in cloudwater droplets. Using the airborne and snowpit concentrations with assumed dry deposition velocities of 0.02–0.05 cms⁻, it is estimated that dry deposition is responsible for roughly 10–30% of the total sulfate deposition on a year-round basis at Dye 3. During portions of the Arctic winter, however, when the snow is unrimed and when there is less precipitation, dry deposition may be dominant.     

The contribution of in-cloud oxidation of SO2 to wet scavenging of sulfur in convective clouds

The sensitivity of in-cloud oxidation of SO₂ in corrective clouds to a number of chemical and physical parameters is examined. The parameterization of precipitation growth processes is based on the work of Scott (1978) and Hegg (1983). A chemical model predicts gas and aqueous phase distributions of soluble gases and in-cloud uncatalyzed oxidation of SO₂ by O₃ and H₂O₂. Sulfate aerosol and SO₂, CO₂, NH₃, H₂O₂ and O₃ gases and their aqueous phase dissociation products are treated.The results indicate that in-cloud conversion is an important removal mechanism for SO₂ and accounts for a significant fraction of the precipitation sulfate. However, except at low SO₂ concentrations, the precipitation sulfate concentration is insensitive to the initial SO₂ concentration; the sulfate concentration is most sensitive to the initial H₂O₂ and NH₃ concentrations. At low SO₂ concentrations, the precipitation sulfate concentration is determined primarily by the initial sulfate aerosol concentration. The feedback between sulfate production and pH is important in limiting SO₂ oxidation by O₃. If gas phase H₂O₂ of order 1 ppb is the major source of aqueous phase H₂O₂ for S(IV) oxidation, it is likely that the oxidation reaction is oxidant limited. The sulfate concentration is a decreasing function of the precipitation rate. At low rainfall rates (< 1 mm h⁻¹), ice phase growth decreases the sulfate concentration. However, the results are insensitive to an ice phase origin at moderate and high rainfall rates.     

Influence of Fe and mn ions on the incorporation of radioactive 35SO2 by sulfate aerosols

The rate of incorporation of radiolabeled sulfur dioxide has been determined in submicron sized ammonium sulfate droplet aerosols with and without catalytic metal ions (Fe³⁺, Mn²⁺). The sulfate droplets were generated by nebulizing solutions with a multiple jet Collison nebulizer and aged up to 30 min in a 10 m³ plug-flow reaction duct. Radiolabeled ³⁵SO₂ was metered into purified air to provide a concentration of 5 ppm.Three different atmospheres were studied: SO₂ in purified air, SO₂ in the presence of ammonium sulfate aerosol (1 mg m⁻³, 1 μm MMAD), and SO₂ in the presence of ammonium sulfate aerosol containing Fe³⁺ and Mn²⁺ ions. No measurable SO₂ conversion was detected in samples from atmospheres without the catalytic metal ions. A net SO₂ conversion rate equivalent to 0.02 % h⁻¹ was observed in the presence of Fe³⁺ and Mn²⁺ ions.     

A Study of Primary Sulfate Emissions From a Coal-Fired Boiler with FGD

A study was carried out to investigate the emissions of SO₂ and primary sulfate materials (H₂SO₄ and inorganic particulate matter) from a boiler burning fossil fuel and using a wet-limestone scrubber for SO₂ removal. Experiments were designed to assess the scrubbing efficiency for SO₂ and sulfate, as well as the potential for scrubber liquor reentrainment. The boiler studied was an 820 MW cyclone-fired unit equipped with a wet, limestone scrubber, consisting of eight two-stage venturi-absorber modules designed to treat a flue gas flow rate of 2,760,000 acfm. The boiler fuel was a low-grade sub-bituminous coal with ash and sulfur contents of 25 and 5%, respectively. Multiple-sampling methods were employed concurrently on the inlet and outlet of a candidate absorber module to measure SO₂, total water-soluble sulfate, and free H₂SO₄. Samples were collected during three field experiments from September 1977 through April 1978. The average SO₂ scrubbing efficiency was 76% and was observed to decrease over the 5 day operation/maintenance cycle of the module. The total water-soluble sulfate input to the scrubber amounted to approximately 1% of the total sulfur oxides and was composed of a 5:1 ratio of H₂SO₄ to particulate sulfate. The total sulfate scrubbing efficiency, averaging about 29%, was invariant with respect to SO₂ removal. The sulfate emissions measured in the scrubber exit gas consisted of about 85 % H₂SO₄ as a fine aerosol. Mass emissions of acid and particulate sulfate were calculated as 1730 Ib/hr and 305 Ib/hr, respectively.     

Sulfate Emissions from Vehicles on the Road

Experiments have been conducted to measure vehicle sulfate emissions, by vehicle type, at two tunnels on the Pennsylvania Turnpike. A satisfactory balance between estimated fuel sulfur consumption and observed emissions of sulfur compounds corrected for ambient-air contributions was obtained. This work started in 1974 before the introduction of catalyst-equipped automobiles and continued into 1976. The sulfate contributed by vehicles even in the tunnels was found to be generally modest relative to rural ambient sulfate levels. Average sulfate emission rates were found to be ~30 mg/km (50 mg/mi) from heavy-duty Diesel trucks, <15 mg/km from catalyst-equipped cars (probably in the range 4 to 7 mg/km), and probably <1 mg/km from non-catalyst cars. The overall SO₂ —* SO₄ ^-2 conversion of the vehicle emissions was 2 %.     

34S/32S Evidence of biogenic sulfur oxides in a salt marsh atmosphere

The use of ³⁴S/³²S measurements to identify the source of atmospheric sulfur oxides was evaluated in a study conducted at a rural salt marsh. δ³⁴S values of SO₂ and non sea salt SO²⁻₄ collected on one side of a large salt marsh were compared with one another and with that of non sea salt SO²⁻₄ collected 4 km away on the opposite side of the marsh. Associations between these values indicated that the measurements were extremely precise and accurate, and that the ground level sulfur cycle was dominated by H₂S produced by bacterial sulfate reducers in anoxic marsh sediments. There was no isotopic evidence of the presence of transported pollutant SO²⁻₄ at this location, although the sampled air masses had passed over very large sources of anthropogenic S and high Particulate V and Pb concentrations confirmed that these air masses were contaminated with pollutant effluents. Biogenic SO²⁻₄ and SO₂ concentrations ranged up to 24.6 and 26μgm⁻³, respectively, and were highest in modified marine-tropical air masses. Associations between concentrations of V and SO²⁻₄ and between Pb and SO₂ suggested the participation of these trace metals (or constituents for which they function as tracers) in the atmospheric oxidation reactions of the sulfides.     

Soot particles and their impacts on the mass cycle in the Tibetan atmosphere

Atmospheric aerosol particles in urban and mountain areas around Lhasa city (29.65°N, 91.13°E) in the Tibetan Plateau were collected in the summers of 1998 and 1999. The particles were analyzed with electron microscopes and an energy dispersive X-ray spectrometer. Individual particle morphology, elemental composition and mixture of sulfate and nitrate were investigated. In the urban area, soot particles emitted from vegetation burning were dominant. These particles were characterized by chain or aggregate morphologies, and an elemental composition of potassium and sulfur. Such particles were frequently detected in mountain areas out of the city, where they formed droplets acting as condensation nuclei. Quantitative estimation indicated that sulfur was accumulated onto the soot particles during their dispersion from the urban area to mountain areas. Sulfate and nitrate detections indicated that soot particles collected in the urban area did not contain nitrate and BaCl₂-reactive sulfate, which revealed that the combination of sulfur and potassium in the particles was not K₂SO₄. In contrast, the particles dispersed to mountain areas contained BaCl₂-reactive sulfate and some contained nitrate, suggesting that soot particles emitted from the urban area could increase the buffering capacity of aerosol particles and enhance the formation of particulate sulfate through heterogeneous conversion in the Tibetan atmosphere.     

Background levels of air and precipitation quality for Europe

This paper is intended to be used by specialists engaged in air and precipitation quality management on regional and continental scales. Major goals are to establish definition, methodology and specific values of background air and precipitation quality for sulfur (S) and nitrogen (N) species to be used in practical applications of air resources management. Major findings are the following:

• 1.(a) 69% of SO₂ and 63 % of NO₂ concentration over Europe originate from continental scale anthropogenic sources,
• 2.(b) 15% of precipitation sulfate and 11% of precipitation nitrate over Europe are contributed by hemispheric background,
• 3.(c) hemispheric background pollution values for Europe were found as 1.25 μg (SO₂-S)m⁻³, 0.80 μg (SO₄²⁻-S)m⁻³, 0.157 mg (SO₄²⁻-S)l⁻¹ and 0.04 mg (NO₃⁻-N)ℓ⁻¹.

     

Characterization of the major chemical species in PM2.5 in the Kaohsiung City,Taiwan

The concentrations and characteristics of the major components in ambient fine particles in the urban city of Kaohsiung, Taiwan were measured and evaluated. PM_2.5 samples were collected using a dichotomous sampler from November 1998 to April 1999 and analyzed for water-soluble ion species using ion chromatography and for carbonaceous species using an elemental analyzer. It was found that SO₄²⁻, NO₃⁻, and NH₄⁺ dominated the identifiable components, and occupied 42.2% and 90.0% of PM_2.5 mass and total dissolved ionic concentrations. Carbonaceous species (organic and elemental carbon) accounted for 20.8% of PM_2.5. The secondary aerosol formed through the NO₂/SO₂ gas-to-particle conversion was estimated based on the sulfur/nitrogen oxidation ratio (SOR/NOR), i.e., sulfate sulfur/nitrate nitrogen to total sulfur/total nitrogen. The average SOR and NOR values were 0.25 and 0.07 for PM_2.5. The high SOR and NOR values obtained in this study suggested that there existed a secondary formation of SO₄²⁻ from SO₂ along with NO₃⁻ from NO₂ in the atmosphere. The secondary organic carbon formed through the volatile organic compound gas-to-particle conversion was estimated from the minimum ratio between organic and elemental carbon obtained in this study, and was found to constitute 40.0% of the total organic carbon for PM_2.5 (6.6% of the particle mass). The results obtained in this study suggest that the formation of secondary aerosols due to conversion from gaseous precursors is significant and important in urban locations.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

微氧环境下无色硫细菌和硫酸盐还原菌脱硫

通过间歇曝气形成微氧环境让SRB和CSB实现共生,使含硫酸盐有机废水中硫酸根最终转化成单质硫达到脱硫目的.研究考察了曝气量对SRB还原和CSB氧化的影响,确定了合适的曝气强度和水力停留时间,使得单质硫占系统内总硫比值最大.实验结果显示,在进水COD/SO42-=2000/1500 mg/L、曝气开关时间为2 s/2 min、生化时间为10 h时,单质硫产率最大,为89.53％,SO42-浓度降至最低值72.7 mg/L,还原率达95.1％,此时脱硫效果较好.     

Electron microscopy of acidic aerosols collected over the northeastern United States

As part of the acid precipitation experiment (APEX) conducted in the northeastern U.S. by the National Center for Atmospheric Research and cooperating universities, aerosols were collected from an aircraft in different seasons, locations and meteorological conditions. Particles were impacted on electron microscope grids for morphological analysis and thin-film chemical tests for sulfate and nitrate. Under most conditions the accumulation mode aerosols (c. 0.1–1.0 μm diameter) collected in the boundary layer were composed of sulfate particles of uniform composition (i.e. an internally mixed aerosol), indicating that individual particle composition could be inferred from bulk measurements. Externally mixed aerosols (i.e. assemblages of different kinds of particles) were found to exist near certain sources (e.g. power plants), in urban plumes, and near fair weather cumulus clouds. Direct evidence of rapid oxidation of SO₂ to H₂SO₄ in cloud droplets was obtained in samples collected near clouds in northern New York and central Illinois, and this represents a potentially major pathway for SO₂ oxidation in the lower troposphere.     

Midwest/western/eastern U.S. precipitation and aerosol sulfate: Differences attributable to natural source inputs?

Factor analysis comparisons between the MAP3S network and Minnesota precipitation chemistry data show marked differences. An assessment of ambient aerosol and precipitation chemistry data obtained at several Colorado and Minnesota sites suggests that natural source inputs may contribute to the sulfate observed in ambient aerosol and at least partly, explain the marked differences of Minnesota and Colorado precipitation chemistry data from that of MAP3S (eastern U.S.). However, a recently proposed mechanism, SO₂ to SO₄ conversion on the surface of dust particles, may be more important than natural sources in explaining western and midwestern precipitation chemistry data. It is concluded that these predominantly non-acidic SO₄ sources may explain the poor association between the H⁺ and SO₄ in many western and some midwestern precipitation chemistry data sets.     

Use of stable sulfur isotopes to identify sources of sulfate in Rocky Mountain snowpacks

Stable sulfur isotope ratios and major ions in bulk snowpack samples were monitored at a network of 52 high-elevation sites along and near the Continental Divide from 1993 to 1999. This information was collected to better define atmospheric deposition to remote areas of the Rocky Mountains and to help identify the major source regions of sulfate in winter deposition. Average annual δ³⁴S values at individual sites ranged from +4.0 to +8.2‰ and standard deviations ranged from 0.4 to 1.6‰. The chemical composition of all samples was extremely dilute and slightly acidic; average sulfate concentrations ranged from 2.4 to 12.2 μeq l⁻¹ and pH ranged from 4.82 to 5.70. The range of δ³⁴S values measured in this study indicated that snowpack sulfur in the Rocky Mountains is primarily derived from anthropogenic sources. A nearly linear relation between δ³⁴S and latitude was observed for sites in New Mexico, Colorado, and southern Wyoming, which indicates that snowpack sulfate in the southern part of the network was derived from two isotopically distinct source regions. Because the major point sources of SO₂ in the region are coal-fired powerplants, this pattern may reflect variations in the isotopic composition of coals burned by the plants. The geographic pattern in δ³⁴S for sites farther to the north in Wyoming and Montana was much less distinct, perhaps reflecting the paucity of major point sources of SO₂ in the northern part of the network.