Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM

A radiation fog physics, gas- and aqueous-phase chemistry model is evaluated against measurements in three sites in the San Joaquin Valley of California (SJV) during the winter of 1995. The measurements include for the first time vertically resolved fog chemical composition measurements. Overall the model is successful in reproducing the fog dynamics as well as the temporal and spatial variability of the fog composition (pH, sulfate, nitrate, and ammonium concentrations) in the area. Sulfate production in the fog layer is relatively slow (1–4 μg m⁻³ per fog episode) compared to the episodes in the early 1980s because of the low SO₂ concentrations in the area and the lack of oxidants inside the fog layer. Sulfate production inside the fog layer is limited by the availability of oxidants in the urban areas of the valley and by SO₂ in the more remote areas. Nitrate is produced in the rural areas of the valley by the heterogeneous reaction of N₂O₅ on fog droplets, but this reaction is of secondary importance for the more polluted urban areas. The gas-phase production of HNO₃ during the daytime is sufficient to balance the nitrate removed during the nighttime fog episodes. Entrainment of air from the layer above the fog provides another source of reactants for the fog layer. Wet removal is one of most important processes inside the fog layer in SJV. We estimate based on the three episodes investigated during IMS95 that a typical fog episode removes 500–2000 μg m⁻² of sulfate, 2500–6500 μg m⁻² of nitrate, and 2000–3500 μg m⁻² of ammonium. For the winter SJV valley the net fog effect corresponds to reductions in ground ambient concentrations of 0.05–0.2 μg m⁻³ for sulfate, 3–6 μg m⁻³ for total nitrate, and 1–3 μg m⁻³ for total ammonium.     

Characterization of polycyclic aromatic hydrocarbons deposition in PM2.5 and cloud/fog water at Mount Taishan (China)

Polycyclic aromatic hydrocarbons (PAHs) in PM2.5 and cloud/fog water samples were collected at Mount Taishan in an autumn–winter period, and were analyzed by GS-MS. Higher molecular weight PAHs (4–6 rings) predominated in PM2.5 samples, whereas lighter PAH compounds contributed 61.71% of the total PAH concentration in cloud/fog samples. Particles tended to contain more PAHs and have a more intensive influence on the atmospheric environment on colder days. During cloud/fog events, the scavenging ratio based on PAHs associated with particles was estimated to be about 13.45%. PAHs in PM2.5 samples had a significant positive relationship with CO and SO₂, suggesting that PAHs, SO₂, and CO may originated from the same sources, such as residential coal combustion activities. Diagnostic ratio analysis and factor analysis indicated that the sources of PAHs were mainly from coal combustion during this period.     

Potential contribution of sulfate production in cumulus cloud droplets to ground level particle sulfur concentrations

The relationships have been examined between the presence or absence of cumulus clouds and 3rd quarter fine particle sulfur concentrations in St Louis. An association between the presence of cumulus clouds with SO₂ conversions in droplets and incrementally higher fine particle sulfur concentrations can be demonstrated. However, diurnal patterns of fine particle sulfur concentrations in the presence of cumulus clouds are not consistent with local contributions from sulfate formation in cumulus clouds. Morning fog often occurs on the same days on which cumulus clouds form later. Reactions of SO₂ in fog droplets appear to make a contribution, but do not account for the major part of the increments in fine particle sulfur concentrations associated with cumulus clouds. The variations in fine particle sulfur concentrations observed can be explained if a substantial part of the sulfate formed in cumulus is transported upwards from the planetary boundary layer into the lower free troposphere. Subsequent multiday regional scale horizontal transport with concurrent gradual vertical transport of sulfate down to the surface would be consistent with the observed results.     

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.     

An Atmospheric Particulate Sampling Procedure For Gravimetric And Elemental Analyses

Large quantities of atmospheric aerosols with compositions SO₄ ⁼, NO₃ ^? and NH₄ ⁺ have been detected in highly industrialized areas. The major portions of aerosol products are the results of energyrelated fuel combustion. Both microphysical and macrophysical processes are considered in investigating the time dependent evolution of the saturation spectra of condensation nuclei associated with both polluted and clean atmospheres during the time periods of advection fog formation. The results show that the condensation nuclei associated with a polluted atmosphere provide more favorable conditions than condensation nuclei associated with a clean atmosphere to produce dense advection fog, and that attaining a certain degree of supersaturation is not necessarily required for the formation of advection fog with condensation nuclei associated with a polluted atmosphere for monodisperse distribution.     

Sulfate and carbonaceous aerosols in Beijing China

Results of our aerosol study, performed during 1983–1984 in Beijing, demonstrate that ambient carbonaceous aerosols are derived principally from coal combustion. Different SO₂ oxidation processes have been observed in summer and winter. The winter sulfate appears to be produced locally and associated with products of incomplete combustion.     

A Simple Model for SO2 Removal in the Duct Injection Process

Abstract

In the In-Duct Injection Process, a lime slurry is sprayed into the flue gas between the air preheater and solids collection equipment, and about 30-60 percent removal of SO₂ is achieved. A simple model of this process has been developed based on heat and mass transfer theories, and this model was fitted to the data obtained at proof-of-concept test units. Data taken with separate injection of dry lime and water were also modeled, but the SO₂ removal was less than for slurry injection, probably because of incomplete capture of lime particles by the water droplets.     

Separate chemical characterizations of fog water,aerosol, and gas before,during, and after fog events near an industrialized area in Japan

Fog water, aerosol, and gas were separately collected at Mt. Rokko (altitude 931 m) in Kobe, Japan, using a new sampling method at a mountainous site near a highly industrialized area. The fog water was collected by an active string-fog collector and the aerosol and gas by using the filter pack method. Using plural filter packs and controlling or switching the airflow before, during, and after a fog event made it possible to collect the fog water, aerosol, and gas separately. Nitrate species such as NO₃⁻(p) and HNO₃(g) were effectively scavenged by fog water, while sulfur species such as SO₄²⁻(p) and SO₂(g) could not be easily and effectively scavenged because of the poor solubility of SO₂(g). This difficulty was experimentally examined through an in situ investigation. Ion species (especially Na⁺(p) and Ca²⁺(p)) which form coarse particles were easily and effectively scavenged by fog water. On the other hand, the difficulty of scavenging Mg²⁺(p) could not be explained by particle size.     

The Contribution of Sulfate and Nitrate to Atmospheric Fine Particles During Winter Inversion Fogs in Cache Valley,Utah

Abstract

Air pollutants were collected in Logan, Cache County, UT, in February 1993 during two periods of atmospheric inversion accompanied by fog. The following atmospheric species were determined: (1) gaseous SO₂, NO₂ (semi-quantitatively),HNO3, NH3, and HF; (2) fine particulate SO₄ ⁼, NO₃ ^-, NH₄ ⁺, F–, H⁺, C, Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Pb, Se, Br, and Sr, and; (3) fine particulate mass, which was calculated. The major components of fine particulate matter were carbonaceous material, ammonium nitrate, and ammonium sulfate, while the soil component was small. Calculated, fine particulate mass averaged 80 μg/m³ and reached concentrations as high as 120 μg/m³. SO₂/So_x and NO₂/NO_y mole ratios generally varied between 0.2 and 0.1 during inversions. These ratios also showed moderate but consistent diurnal patterns. The emission inventory for Cache County indicates sources of SO₂ and NO_x but not significant amounts of primary sulfate and nitrate. The observations reported here indicate there is significant conversion of SO₂ and NO_x in the presence of excess oxidants to sulfuric and nitric acid that are neutralized by excess ammonia.     

A Versatile Electrochemical Monitor for Air-Quality Measurements

An electrochemical instrument of the type commonly used to monitor total oxidants was adapted to measure acid gases such as SO₂, HCI, and HCO₂H. By using chemical methods of treating the air sample prior to absorption, it is possible to monitor for specific oxidants and acids. Measurements of NO, NO_x, and SO₂ during smog-chamber experiments were found to be in good agreement with measurements made by other methods.     

Modeling of Potential Power Plant Plume Impacts on Dallas-Fort Worth Visibility

ABSTRACT

During wintertime, haze episodes occur in the Dallas-Ft. Worth (DFW) urban area. Such episodes are characterized by substantial light scattering by particles and relatively low absorption, leading to so-called “white haze.” The objective of this work was to assess whether reductions in the emissions of SO₂ from specific coal-fired power plants located over 100 km from DFW could lead to a discernible change in the DFW white haze. To that end, the transport, dispersion, deposition, and chemistry of the plume of a major power plant were simulated using a reactive plume model (ROME). The realism of the plume model simulations was tested by comparing model calculations of plume concentrations with aircraft data of SF₆ tracer concentrations and ozone concentrations. A second-order closure dispersion algorithm was shown to perform better than a first-order closure algorithm and the empirical Pasquill-Gifford-Turner algorithm. For plume impact assessment, three actual scenarios were simulated, two with clear-sky conditions and one with the presence of fog prior to the haze. The largest amount of sulfate formation was obtained for the fog episode. Therefore, a hypothetical scenario was constructed using the meteorological conditions of the fog episode with input data values adjusted to be more conducive to sulfate formation. The results of the simulations suggest that reductions in the power plant emissions lead to less than proportional reductions in sulfate concentrations in DFW for the fog scenario. Calculations of the associated effects on light scattering using Mie theory suggest that reduction in total (plume + ambient) light extinction of less than 13% would be obtained with a 44% reduction in emissions of SO₂ from the modeled power plant.     

Characterization of size segregated particles collected over Alaska and the CAnadian high Arctic,AGASP-II flights 204–206

Ten aircraft-collected cascade impactor samples from the North American Arctic were analyzed using analytical electron microscopy. Morphological, mineralogical and elemental information were obtained from individual particles, as well as compositional data and size distribution estimates of the bulk aerosol. Categorization of carbonaceous material into organic-type and combustion-type carbon particles was performed in this study. This was accomplished through the use of a new ultra-thin window X-ray spectrometer, which can directly detect carbon X-rays emitted from particles, and through interpretation of morphological and electron diffraction data. Verification of graphite as a specific carbon mineral phase present in Arctic soot particles was performed in this manner.Several classes of particles were present in most of the aerosol samples and size fractions. These included liquid H₂SO₄ droplets, which were always present in the highest numbers, and crustal-type and composite SO₄⁻² particles. A small fraction (0–30%) of a random sampling of SO²⁻₄particles from all impactor stages were found to contain detectable nitrogen, suggesting that partial neutralization by NH₃ may have occurred in this minority of the SO²⁻₄ droplets. Particles rich in non-combustion carbon and thought to be composed of organic material were also observed in most samples. Haze samples collected off the coast of Alert, NWT, show moderate loadings of H₂SO₄ droplets. Judging from these loadings and those from higher-altitude samples, ambient aerosol particle concentrations must have been considerably higher in the haze. The extent to which local activity at Alert has influenced these haze samples is not known, although a major contribution is not expected. Stratospheric samples did not contain several classes of particles thought to have major anthropogenic source inputs to the Arctic, such as black carbon and coal-fired combustion spheres. The lightest particle loadings in any samples were collected in the upper troposphere near the tropopause, where condensation nuclei counts during sampling fell to as low as 10 cm⁻³.     

Simultaneous Control of Hg0, SO2, and NOx by Novel Oxidized Calcium-Based Sorbents

Abstract

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg⁰), SO₂, and NO_x removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg⁰, SO₂, and NO_x capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg⁰ sorp-tion capacities (~100 μg/g) comparable to that of the activated carbon; they showed far superior SO₂ and NO_x sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg⁰, SO₂, and NO_x emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.     

A model of sulphate production in a cap cloud and subsequent turbulent deposition onto the hill surface

A model has been constructed of the dynamics and microphysics of a hill cap cloud. This has been used to investigate the aqueous phase oxidation of SO₂ in the cloud droplets and the subsequent turbulent deposition of chemical species onto the hill surface. It is suggested that the dominant oxidant is H₂O₂ in these clouds and that therefore the process is likely to be oxidant limited. The amount of sulphate produced is comparable to that found in cloud condensation nuclei typically found over the U.K. and elsewhere away from strong local sources of sulphate aerosol. Ammonia concentrations are very important as they alter the cloud water pH and hence the solubility of SO₂.Turbulent or ‘occult’ deposition is very sensitive to wind speed, the stability profile of the atmosphere and to the surface roughness. In a supercritical flow regime the occult deposition is a maximum just on the lee of the hill.     

A computer modelling study of the chemistry occurring during cloud formation over hills

A model has been developed which describes the chemical processes occurring during the formation of hill cloud. This model has been applied to the study of four cases which should be typical of the chemical conditions which can exist during the formation of such cloud over hills in the N of England.The results show that a wide range of chemical behaviour is possible in cloud droplets, depending on the history of the airmass. The composition of the water-soluble aerosol is of importance in determining the chemical composition of cloud droplets, with most of the sulphate and large proportions of the other ions being derived from this source. Gas-phase chemistry is also important, not only because it dictates the initial concentrations of oxidants such as H₂O₂ and O₃ and of acidic gases such as HNO₃ at the onset of condensation, but also because of the chemical processes which occur concurrently with those in clouds. These are important sources of radicals, as well as of nitric acid, which continue to dissolve in solution. Gasphase HCl, HNO₃ and NH₃ are all of primary importance in describing the acidity of cloud droplets. The various oxidation mechanisms for SO₂ can all be important, with their relative contributions varying from case to case. H₂O₂ does not invariably dominate this process, especially in winter when its concentration may be low.The chemistry of hill clouds is far from trivial and oversimplification can result in a misunderstanding of the behaviour which occurs. There is a need, rather, to consider a wide range of reactions if the nature of the overall processes and the impact of manmade emissions on the environment via this route are to be understood.     

Contribution of transboundary air pollution to ionic concentrations in fog in the Kinki Region of Japan

To estimate the contribution of transboundary transported air pollutants from other Asian countries to Japan in ionic concentrations in fog water in March 2005, the Community Multiscale Air Quality (CMAQ) modeling system was utilized with meteorological fields produced by the 5th generation Mesoscale Model (MM5). For meteorological predictions, the model well reproduced the surface meteorological variables, particularly temperature and humidity, and generally captured fog occurrence. For chemical predictions, most of the model-predicted monthly mean concentrations were approximately within a factor of 2 of the observations, indicating that the model well simulated the long-range atmospheric transport from the Asian Continent to Japan. For SO₄^2?, NO₃^? and NH₄⁺, the contribution rates of the transboundary air pollution in the Kinki Region of Japan ranged from 69 to 82% for aerosols, from 47 to 87% for ionic concentrations in rain, and from 55 to 79% for ionic concentrations in fog. The study found that the transboundary air pollution also affected ionic concentrations in fog as well as aerosol concentrations and ionic concentrations in rain.     

Reaction behavior of SO2 in the sintering process with flue gas recirculation

The primary goal of this paper is to reveal the reaction behavior of SO₂ in the sinter zone, combustion zone, drying–preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO₂ retention in the sinter zone was associated with free-CaO in the form of CaSO₃/CaSO₄, and the SO₂ adsorption reached a maximum under 900ºC. SO₂ in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO₂ adsorption in the sintering bed mainly occurred in the drying–preheating zone, adsorbed by CaCO₃, Ca(OH)₂, and CaO. When the SO₂ adsorption reaction in the drying–preheating zone reached equilibrium, the excess SO₂ gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)₂ and H₂O. The emission rising point of SO₂ moved forward in combustion zone, and the concentration of SO₂ emissions significantly increased in the case of flue gas recirculation (FGR) technique.

Implications: Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO₂ emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO₂ emissions because it will directly influence the demand and design of the FGD system.     

On the difference between SO2−4 and NO−3 in wintertime precipitation

Winter rains have lower NO⁻₃ levels but higher SO²⁻₄ levels than snows in the NE United States. In this study, four years of winter precipitation data from SE Michigan were examined to help understand these differences. Although NO⁻₃ levels were indeed higher in snow than winter rain, the higher concentrations could be attributed to the generally lower precipitation depths associated with snow events than with rain events. The NO⁻₃ concentrations are inversely correlated with precipitation depth. There was no evidence that snow scavenged HNO₃ in the air more efficiently than rain.Conversely, SO²⁻₄ was far higher in winter rain than in snow. This could not be explained in terms of ground-level ambient S concentrations or the wind direction from which the storm originated. However, the cloud temperatures were high enough in the case of rain to suggest that the cloud hydrometeors could have been present as liquid droplets rather than ice crystals. The SO²⁻₄ concentrations of the precipitation were highly correlated with the temperatures of the cloud layers. The data suggest that SO₂ is incorporated and oxidized to SO²⁻₄ in clouds most efficiently when the hydrometeors are present as liquid droplets. The fact that NO⁻₃does not show the same relationship suggests that incorporation of N species into cloud water followed by oxidation is not as important a process for N as for S.     

Non-linear response of wet deposition to emissions reduction: A model study

An Eulerian atmospheric model with complex chemistry (Acidic Deposition and Oxidant Model) and a Lagrangian model with linear chemistry (Ontario Ministry of the Environment Trajectory Model) were used to simulate the wet SO₄²⁻ deposition pattern over eastern North America for 16 days during April 1981.The two model results agree reasonably well with each other when the 16 day average values are compared. They also show reasonable agreement with observed data. Having established the ability of the models to predict deposition patterns for 1981 emissions, reduction scenarios with 50% SO_x and 50% SO_x and NO_x of the 1981 emissions were studied through the Eulerian model. Near the heavy emissions area, the reduction in SO₄²⁻ wet deposition is only about 30–40%. In this respect the linear Lagrangian model departs significantly from the Eulerian model. This non-linearity in response is attributed to the role of oxidants in controlling the conversion of SO₂ to SO₄²⁻.     

Observations and modelling of aerosol growth in marine stratocumulus—case study

Airborne measurements of the growth of the marine accumulation mode after multiple cycles through stratocumulus cloud are presented. The nss-sulphate cloud residual mode was log-normal in spectral shape and it’s mode radius was observed to progressively increase in size from 0.78 to 0.94 μm over 155 min of air parcel evolution through the cloudy marine boundary layer. The primary reason for this observed growth was thought to result from aqueous phase oxidation of SO₂ to aerosol sulphate in activated cloud drops. An aqueous phase aerosol–cloud-chemistry model was used to simulate this case study of aerosol growth and was able to closely reproduce the observed growth. The model simulations illustrate that aqueous phase oxidation of SO₂ in cloud droplets was able to provide enough additional sulphate mass to increase the size of activated aerosol. During a typical cloud cycle simulation, ≈4.6 nmoles kg^-1_air (0.44 μg m^-3) of sulphate mass was produced with ≈70% of sulphate production occurring in cloud droplets activated upon sea-salt nuclei and ≈30% occurring upon nss-sulphate nuclei, even though sea-salt nuclei contributed less than 15% to the activated droplet population. The high fraction of nss-sulphate mass internally mixed with sea-salt aerosol suggests that aqueous phase oxidation of SO₂ in cloud droplets activated upon sea-salt nuclei is the dominant nss-sulphate formation mechanism and that sea-salt aerosol provides the primary chemical sink for SO₂ in the cloudy marine boundary layer.