Simulation of long-range transport of acidic pollutants in East Asia during the Yellow Sand event

The atmospheric chemical process was simulated using the Carbon Bond 4 (CB-4) model, the aqueous-phase chemistry in Regional Acid Deposition Model and the thermodynamic equilibrium relation of aerosols with the emission inventories of the Emission Database for Global Atmospheric Research, the database of China and South Korea and the Mesoscale Model version 2 (MM5) meteorological fields to examine the spatial distributions of the acidic pollutant concentrations in East Asia for the case of the long-lasting Yellow Sand event in April 1998. The present models simulate quite well the observed general trend and the diurnal variation of concentrations of gaseous pollutants, especially for O₃ concentration. However, the model underestimates SO₂ and NO_x concentration but overestimates O₃ concentration largely due to uncertainty in NO_x and VOC emissions. It is found that the simulated gaseous pollutants such as SO₂, NO_x, and NH₃ are not transported far away from the source regions but show significant diurnal variations of their concentrations. However, the daily variations of the concentrations are not significant due to invariant emission rates. On the other hand, concentrations of the transformed pollutants including SO₄²⁻, NH₄⁺, and NO₃⁻ are found to have significant daily variations but little diurnal variations. The model-estimated deposition indicates that dry deposition is largely contributed by gaseous pollutants while wet deposition of pollutants is mainly contributed by the transformed pollutants.     

Modelling the atmospheric transport and deposition of sulphur and nitrogen over the United Kingdom and assessment of the influence of SO2 emissions from international shipping

A statistical Lagrangian atmospheric transport model was used to generate annual maps of deposition of sulphur and oxidised and reduced nitrogen for the UK at a 5×5 km² resolution. The model was run using emissions for the year 2002. The model was compared with measurements of gas concentrations (SO₂, NO_x, HNO₃ and NH₃) and of wet deposition and aerosol concentrations of SO₄²⁻, NO₃⁻ and NH₄⁺ from national monitoring networks. Good correlation was obtained, demonstrating that the model is capable of accurately estimating the mass balance and spatial distribution of sulphur and nitrogen compounds in the atmosphere. A future emissions scenario for the year 2020 was used to test the influence of shipping emissions on sulphur deposition in the UK. The results show that, if shipping emissions are assumed to increase at a rate of 2.5% per year, their relative contribution to sulphur deposition is expected to increase from 9% to 28% between 2002 and 2020. The model was compared to both a European scale and a global scale chemical transport model and found to give broad agreement with the magnitude and location of sulphur deposition associated with shipping emissions. Enforcement of the MARPOL convention to reduce the sulphur content in marine fuel to 1% was estimated to result in a 6% reduction in total sulphur deposition to the UK for the year 2020. The percentage area of sensitive habitats with exceedance of critical loads for acidity in the UK was predicted to decrease by 1% with the implementation of the MARPOL convention.     

An Eulerian transport/transformation/removal model for so2 and sulfate—II. Model calculation of SOx transport in the eastern United States

A three-dimensional, time dependent Eulerian transport/transformation/removal model for SO_x, which has previously been described is applied to the eastern United States. Simulation results for a 72-h simulation using 4 July 1974 meteorological data consisting of 24-h averaged SO₂ and sulfate contours, deposition contours, reaction rate contours, and diurnal SO₂ and sulfate ground level profiles are presented and discussed. Substantial spatial and temporal variations in the distributions of SO₂ and sulfate are predicted and results indicate that relatively detailed vertical resolution is necessary in studying the regional transport of SO_x. The presented results illustrate the model's capability to simulate the interactions between emissions, transport, chemistry and surface removal.     

The sensitivity of a 3-dimensional Eulerian model to uncertainties in emissions and dry deposition velocities

A 3-dimensional STEM-I Eulerian, regional scale transport/chemistry model for SO₂ and sulfate is used to investigate the relationships between model predictions and the resolution and uncertainty in the emissions and dry deposition velocities. Model results for conditions of 4 July 1974 where the emissions are time modulated, where the emissions are increased and decreased, and where the dry deposition velocities are increased and decreased are presented and discussed.     

On the episodic nature of wet deposited sulphate and acidity

Daily sampling of acidity and sulphate in rain, air concentrations of SO₂ and aerosol SO₄²⁻, and climatological variables for the period 1977 to 1981 at a site in southern Scotland are analysed. The properties of frequency distributions for wet deposited acidity, sulphate and rainfall, and the episodicity of each, are discussed. Up to 40% of annual wet deposited acidity occurred on < 4% of rain days, exceeding the episodicity of dry deposited SO₂ by a factor of 3.Over the 5 year period, 16 % of rain events were more acid than pH 4.0 and 25 % less acid than pH 5.0; meteorological conditions associated with these extremes of the distribution showed marked differences. The most acid events were associated with large aerosol SO₄²⁻ concentrations, small windspeeds and rainfall amounts, and 48-h surface geostrophic wind back-trajectories over industrial regions of the U.K. and/or Europe. The least acid events were associated with 48-h back-trajectories over the north Atlantic, larger windspeeds and rainfall amounts. The very acid events are well described by the frequency distribution of rainfall acidity.Artefacts in rainfall chemistry data caused by dry deposition on the collector are discussed with particular reference to the variation of SO₄²⁻ concentration with rainfall amount.     

Wet and dry deposition monitoring in Southeastern Michigan

Wet and dry deposition as collected by a bucket were measured at two sites in southeastern Michigan for two years. The precipitation had an average pH of 4.27 and a SO²⁻₄ to NO⁻₃ ratio of 2.0. Particulate dry deposition velocities of 0.6 cm s⁻¹ for SO²⁻₄ and NO⁻₃ and > 2 cm s⁻¹ for Cl⁻, Ca²⁺, Mg²⁺,Na⁺ and K⁺ were calculated. The ambient particle composition, dry bucket collection and wet deposition were compared at two sites, one urban and the other rural. Higher ambient particle concentrations and dry deposition rates were measured at the urban site than the rural site, indicating the influence of local emissions. However, local emissions had no effect on the wet deposition concentrations. The influence of more distant source regions was examined by separating the precipitation events by wind direction. The events from the south and east had the highest SO²⁻₄ to NO⁻₃ ratios, which corresponded to the areas with the highest sulfur emissions. NO⁻₃ showed no directional dependence.Wet deposition was examined for the effect of storm type and seasonal trends. Contrary to a recent study on Long Island, we found higher concentrations of H⁺, SO²⁻₄ and NH⁺₄ in winter rain compared to snow. The wet deposition concentrations of H⁺, SO²⁻₄, and NH⁺₄ were highest in the summer, while only Na⁺ and Cl⁻ concentrations were highest in the winter, presumably due to winter road salting. The total deposition of acidic ions was highest in the summer and lowest in the winter, due both to lower concentrations and lower precipitation volumes in the winter. The dry deposition as collected by a bucket accounted for 1 % of total H⁺ deposition, 21 % of SO²⁻₄ deposition, 27% of NO⁻₃ deposition, 50% of Cl⁻ deposition and 61 % of Ca²⁺ deposition.     

Wet and dry deposition of sulfur and nitrogen compounds in Ontario

Measurements have been made of sulfur and nitrogen compounds in precipitation since 1980 and in air since 1981 in Ontario. This paper presents results of the atmospheric deposition measurement program to the end of 1985. As is to be expected from the distribution of emission sources, annual concentrations of SO₄²⁻ andNO₃⁻ in precipitation, and of SO₂,SO₄²⁻ andNO₃⁻ in air are higher in southern Ontario than in northern Ontario. The corresponding distribution pattern for deposition is similar to that of concentration. A wet SO₄²⁻ deposition rate of 20 kg ha¹⁻ y¹⁻, a value considered critical for the acidification of sensitive water bodies, is exceeded in all of central and southern Ontario. On a province-wide basis, sulfur wet deposition is about four times higher than sulfur dry deposition. For nitrogen, wet and dry deposition are more comparable, though the former is still higher. The S- and N-species display different seasonal trends in concentration and deposition reflecting a dependence on meteorological factors, and on the associated chemical transformation rates. On the other hand, year to year variations are small.     

Regional-scale impacts of Phase I of the Clean Air Act Amendments in the USA: the relation between emissions and concentrations,both wet and dry

A comparison of data records in the 1990s, both before (1991–1994) and after (1995–1997) implementation of Phase I of the Clean Air Act Amendments (CAAA) of 1990 for the eastern US, shows a significant reduction in SO₂ emissions for most states, except for Texas, North Carolina, Illinois, Florida, and Alabama. However, of the major NO_x emitting states, only two eastern states (New York and Pennsylvania) show significant declines in NO_x. A pattern of large declines in SO₂ emissions (>20%) after CAAA implementation, and large declines in precipitation SO₄²⁻ and H⁺, as well as air concentrations of SO₂ and SO₄²⁻ (components of dry deposition), exists for most regions of the eastern US. In most cases, the emission/concentration relations are close to 1 : 1 when the source region based on 15-h back trajectories is used for the New England region, and source regions based on 9-h back trajectories are used for the six other eastern US regions that were studied. The southern Appalachian Mountain region, an acid-sensitive area receiving high levels of acidic deposition, has not seen an appreciable improvement in precipitation acidity. This area has also shown the least improvement in wet and dry sulfur concentrations, of the areas examined. Precipitation base cations (Ca²⁺ and Mg²⁺) show a pattern of either increasing or level concentrations when comparing 1990–1994 to 1995–1998 data, for six of the seven regions examined. Ammonium concentrations have generally changed <10%, except for the Illinois and southern Appalachian Mtn. regions, which increased >15%.     

Numerical studies of acidification processes within and below clouds with a flow-through chemical reactor model

A flow-through chemical reactor model has been exercised to assess the importance of various oxidation reactions and cloud processes on wet removal and redistribution of atmospheric pollutants and to investigate the effect of in-cloud acidification on precipitation chemistry at the surface. Preliminary results indicate that in-cloud acidification accounts for more than 60% of the wet deposited acids derived from acidification of initial SO₂, that 42–57% of water-soluble, non-reactive NH₃ and HNO₃ are removed by wet deposition. The pseudo-first-order conversion rate of SO₂ to SO₄²⁻ ranges from 3 to 25% h ⁻¹ depending on initial and boundary conditions.Sensitivity studies have been carried out to test the importance of time evolution of clouds on partitioning of pollutants in the atmosphere and to investigate the variability of precipitation chemistry due to changes in rate constants. The distributions of NH₃ and HNO₃ are found to be dependent largely on the cloud microphysical parameters, while the distributions of H₂O₂ and SO₂ depend largely on initial conditions of both species. Individual physical and chemical mechanisms can determine the overall rate of sulfate wet deposition at different stages of cloud evolution.     

Indications of nonlinearities in processes of wet deposition

Numerical simulations have been carried out with a model consisting of clear-air chemistry, in- cloud chemical reactions, and dynamic processes of cloud development in order to examine the time history of cloudwater pH and sulfate production in a cumulus cloud and the relationship between pollutant precursors and corresponding acidic chemical species in wet deposition. Preliminary results indicate that the molar ratio SO₄²⁻/NC₃⁻ in cloud water increases as the ratio SO₂/NO₂ increases, that the relationship between the increase of precursor SO₂/NO₂ and the increase of SO₄²⁻/NO₃⁻ in cloud water is nonlinear, and that the degree of this nonlinearity becomes more significant for cases when the cloud condensation nuclei content in air is assumed to be invariant.     

Assessing decadal changes in rainwater alkalinity at a rural Mediterranean site in the Montseny Mountains (NE Spain)

Annual volume-weighted mean (VWM) concentrations in rainwater collected at La Castanya (LC, Montseny Mountains, NE Spain) were analysed from 1983 to 2000 to study the temporal trends in precipitation chemistry, and the causes behind the changes. A significant positive correlation was found between annual rainwater SO₄²⁻ concentrations at LC and Spanish SO₂ emissions (r=0.73, P=0.0008) both decreasing remarkably during this period. Rainwater alkalinity increased during the period, shifting from negative values at the beginning (VWM in the 5 initial years=−2.7 μeq l⁻¹) to alkaline values in recent years (VWM in the 5 final years=18.0 μeq l⁻¹). Stepwise regression analysis indicated that 88% of the variation of alkalinity could be accounted for by the variability of non-marine Ca²⁺ and non-marine SO₄²⁻, with a more prominent dependence on Ca²⁺.Rains of African provenance were highly enriched in alkalinity and Ca²⁺, but no significant increases in their occurrence were found for the study period. Because of the reported higher dust updraft in northern Africa during years of high North Atlantic Oscillation (NAO) index, we also explored the relationship between rainwater variables associated with an African provenance and NAO. Annual precipitation was inversely related to NAO (r=−0.61, P=0.007). The annual wet deposition of African dust-related elements showed no correlation with NAO, probably because wet deposition of these elements depends on two factors (precipitation and dust updraft) which have opposite behaviour with respect to NAO. We hypothesise that dry deposition of African dust during dry spells (not sampled in this study) might be higher during high NAO-index years.     

The Danish eulerian hemispheric model — a three-dimensional air pollution model used for the arctic

A three-dimensional Eulerian hemispheric air pollution model, the Danish Eulerian Hemispheric Model (DEHM), is in development at the National Environmental Research Institute (NERI). The model has been used to study long-range transport of air pollution in the Northern Hemisphere. The present version of the model includes long-range transport of sulphur dioxide (SO₂) and particulate sulphate (SC₄²⁻. The chemistry in the model is described by a simple linear oxidation of SO₂ to SO₄²⁻, and the wet deposition of SO₂ and SO₄⁻ is estimated based on the amount of precipitation, which is calculated from the contents of liquid cloud water (see Christensen, Air Pollution Modelling and its Applicatioons, Vol. X, pp. 119–127, Vol. XI, pp. 249–256, Plenum press, New York; 1995, Ph.D. thesis, National Environmental Research Institute, Denmark). The model has been used to study the air pollution in the Arctic. Results from yr simulation with an analysis of the results is presented: the model results are verified by comparisons, to measurements not only from the Arctic region but also from Europe and Canada. Some examples of episodes in the Arctic including analysis of the meteorological conditions during the episodes are presented. Finally, the model has been used to estimate the contribution from the different source regions on the northern hemisphere to the Arctic sulphur pollution.     

Analysis of emission databases for regional models

General procedures for adapting emission inventories to regional models and for studying the impact of differences in inventories on model predictions are outlined. To illustrate the methods, analysis of two inventories which are still being validated is presented. The inventories together satisfy current requirements for the NCAR regional acid deposition model (RADM). These include anthropogenic emissions of SO₂, sulfate aerosol, NO, NO₂, NH₃ and volatile organic compounds (VOC) in 10 reactivity classes, from United States and Canadian point and area sources on 80-km grid resolutions, for weekend and weekday seasonally representative days on a diurnal basis during the 1980–1982 period. Application of checking procedures, designed by our group to screen for subtle anomalies not identified at previous stages of quality assurance employed by the inventory developers, resulted in adjustments primarily to VOC emissions. Comparisons of the modified inventories, which provide an indication of uncertainties in emissions due to variations in inventory development procedures, revealed differences in the eastern United States total daily emissions to be at most on the order of 5 % for SO_x, and NO_x, 20% for VOC and 85% for NH₃. Studies of the impact of inventory differences on predictions of RADM were conducted for the 22–24 April 1981 period, which was monitored as part of the Oxidation and Scavenging Characteristics of April Rains program. Event total wet sulfate deposition differed by 10% or less while midday O₃ concentrations differed by 1% or less for individual grids over the modeling domain.     

The water-soluble ionic composition of PM2.5 in Shanghai and Beijing,China

A year-long field study to characterize the ionic species in PM2.5 was carried out in Shanghai and Beijing, China, in 1999–2000. Weekly samples of PM2.5 were collected using a special low flow rate (0.4 l min⁻¹) sampler. In Shanghai, SO₄²⁻ NO₃⁻ and NH₄⁺ were the dominant ionic species, which accounted for 46%, 18% and 17% of the total mass of ions, respectively. Local SO₂ emissions were an important source of SO₄²⁻ in PM2.5 because the SO₄²⁻ concentration was correlated with the SO₂ concentration (r=0.66). The relatively stable SO₄²⁻/SO₂ mass ratio over a large range of temperatures suggests that gas-phase oxidation of SO₂ played a minor role in the formation of SO₄²⁻. The sum of SO₄²⁻ and NO₃⁻ was highly correlated with NH₄⁺ (r=0.96), but insufficient ammonium was present to totally neutralize the aerosol. In Beijing, SO₄²⁻, NO₃⁻ and NH₄⁺ were also the dominant ionic species, constituting 44%, 25% and 16% of the total mass of water-soluble ions, respectively. Local SO₂ emissions were an important source of SO₄²⁻ in the winter since SO₄²⁻ was correlated with SO₂ (r=0.83). The low-mass SO₄²⁻/SO₂ ratio (0.27) during winter, which had low humidity, suggests that gas-phase oxidation of SO₂ was a major route of sulfate formation. In the summer, however, much higher mass ratios of SO₄²⁻/SO₂ (5.6) were observed and were ascribed to in-cloud sulfate formation. The annual average ratio of NO₃⁻/SO₄²⁻ was 0.4 and 0.6 in Shanghai and in Beijing, respectively, suggesting that stationary emissions were still a dominant source in these two cities.     

Effects of dry deposition on the concentration-distributions of atmospheric pollutants within land- and sea-breeze circulations

In a land- and sea-breeze situation, effects of dry deposition on the dynamics of the concentrations of chemically reacting air pollutants are investigated using a transport/transformation/removal model with diurnally varying deposition velocities modeled in terms of the aerodynamic, surface, and residual resistances. The results show that the diurnally varying flows and eddy diffusivities, which are characteristic of the landand sea-breeze system, transfer the effects of dry deposition on the concentrations quickly to the upper layer over the land and sea surfaces. The dry deposition effect on one species can be transmitted to others through the network of chemical reactions, e.g. inclusion of dry deposition into the simulation resulted in the increase of hydrocarbon concentrations. It is also predicted that the dry deposition processes could remove a considerable part of emitted NO_x, and SO₂ from the local circulations, e.g. for 2 days about 40% of the emitted NO_x was removed by the dry deposition of NO, NO₂, HNO₃ and PAN and in the case of SO₂, 25 % by that of SO₂ and SO₄²⁻.     

Space–time analysis of precipitation-weighted sulfate concentrations over the eastern US

This paper illustrates a simple technique of performing space–time analysis of precipitation-weighted SO₄²⁻ concentration data across the eastern US that were collected by the National atmospheric deposition program. Using a moving average filter and two-dimensional spatial data filtering algorithm on the time series of precipitation-weighted SO₄²⁻ concentrations, we show that decreases of about 50% have occurred in SO₄²⁻ concentrations in Minnesota, Wisconsin, and over the northeastern US between 1985 and 1998, generally consistent with SO₂ emissions’ reductions over this period. The decreases in SO₄²⁻ concentrations tended to be smaller in the midwest and south.     

Seasonal variations in atmospheric SOx and NOy species in the adirondacks

This paper reports the results of over 2 years of measurements of several of the species comprising atmospheric SO_x (=SO₂+SO₄²⁻) and NO_y (=NO+NO₂ + PAN + HNO₃+NO₃⁻+ organicnitrates + HONO + 2N₂O₅ …) at Whiteface Mountain, New York. Continuous real-time measurements of SO₂ and total gaseous NO_y provided data for about 50% and 65% of the period, respectively, and 122 filter pack samples were obtained for HNO₃, SO₂ and aerosol SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺. Concentrations of SO₂ and NO_y were greatest in winter, whereas concentrations of the reaction products SO₄²⁻ and HNO₃were greatest in summer. The seasonal variation in SO₄²⁻ was considerably more pronounced than that of HNO₃and the high concentrations of SO₄²⁻ aerosol present in summer were also relatively more acidic than SO₄²⁻ aerosol in other seasons. As a result, SO₄²⁻ aerosol was the predominant acidic species present in summer, HNO₃was predominant in other seasons. Aerosol NO₃⁻ concentrations were low in all seasons and appeared unrelated to simultaneous NO_y and HNO₃concentrations. These data are consistent with seasonal variations in photochemical oxidation rates and with existing data on seasonal variations in precipitation composition. The results of this study suggest that emission reductions targeted at the summer season might be a cost-effective way to reduce deposition of S species, but would not be similarly cost-effective in reducing deposition of N species. kwAcid deposition, seasonal variation, sulfate, nitrate, nitric acid, sulfur dioxide, oxides of nitrogen, hydrogen peroxide, ozone, air pollution, Adirondack Mountains     

A simulation of sulfur wet deposition and its dependence on the inflow of sulfur species to storms

Numerical precipitation scavenging models are used to investigate the relationship between the inflow concentrations of sulfur species to precipitation systems and the resulting sulfur wet deposition. Simulations have been made for summer and winter seasons using concentration ranges of SO₂, aerosol SO₄²⁻, H₂O₂ and O₃ appropriate for the eastern U.S. summer simulations use one-dimensional timedependent convective cloud and scavenging models; winter simulations use two-dimensional steady-state warm-frontal models. Sulfur scavenging mechanisms include nucleation scavenging of aerosol, aqueous reactions of H₂O₂, O₃ and HCHO with S(IV), and nonreactive S(IV) scavenging. Over the wide range of conditions that have been examined, the relation between sulfur inflow and sulfur wet deposition varies from nearly linear to strongly nonlinear. The degree of nonlinearity is most affected by aerosol SO₄²⁻ levels and relative levels of SO₂ vs H₂O₂. Higher aerosol SO₄²⁻ levels (as found in summer) produce a more linear relation. The greatest nonlinearity occurs when SO₂ exceeds H₂O₂. Winter simulations show more nonlinearity than summer simulations.     

An investigation of the assumptions of linear chemistry and superposition in LRTAP models

Most current LRTAP models assume a linear relationship between sulphur emissions and predicted acidic concentrations, as well as the ability to superpose concentrations from different emission sources. This paper uses a non-linear chemistry model and control scenarios of 50% reductions in S, N and hydrocarbon (HC) emissions to examine the validity of these two assumptions at various downwind receptors. The model predicts that a 50% reduction in S emissions will lead to a 60–65% reduction in SO₂ concentrations and a 25–40% reduction in H₂SO₄ concentrations, depending upon whether or not NO_x and/or HC emissions are reduced by 50% at the same time. The non-linearities in the model predictions are due to complex interactions between NO_x, HC, OH and HO₂. Even when there was non-linearity in the individual S species (SO₂ and SO₄), there was little non-linearity in total airborne S. Adding the results of independent model predictions for different sources (superposition) might introduce errors due to

• 1.(1) chemical interactions between the emissions from the various sources
• 2.(2) overestimates of physical processes such as mixing in of ambient air.

The model was also used to examine trends in regional air quality in eastern North Amierica.