Acid deposition: Perspectives in time and space

Most acid-deposition investigations have been concerned with the impact of nitrogen oxides (NO_x) and sulfur dioxide (SO₂) emissions on Europe and North America. This paper examines three issues beyond this central focus. Major conclusions are 1) ammonia (NH₃) emissions and subsequent nitrogen (N) accumulation in terrestrial ecosystems have the potential to generate significant acidification in terrestrial and aquatic ecosystems; 2) sulfur (S) and N accumulation in environmental reservoirs will not only result in significant and extensive acidification but will also impact the earth's radiation balance, tropospheric oxidizing capacity, ecosystem nutrient balance and groundwater quality; and 3) future emissions will substantially increase in the developing world, especially in Asia. By 2020, Asian emissions of SO₂, NO_x and NH₃ will be equal to or greater than the combined emissions from Europe and North America.     

Projections of SO2, NOx,NH3 and VOC Emissions in East Asia Up to 2030

Starting from an inventory of SO₂, NO_x, VOC and NH₃ emissions for the years 1990 and 1995 in East Asia (Japan, South and North Korea, China, Mongolia and Taiwan), the temporal development of the emissions of the four air pollutants is projected to the year 2030 based on scenarios of economic development. The projections are prepared at a regional level (prefectures or provinces of individual countries) and distinguish more than 100 source categories for each region. The emission estimates are presented with a spatial resolution of 1×1 degree longitude/latitude. First results suggest that, due to the emission control legislation taken in the region, SO₂ emissions would only grow by about 46 percent until 2030. Emissions of NO_x and VOC may increase by 95 and 65 percent, respectively, mainly driven by the expected increase in road traffic volume. Ammonia, mainly emitted from agriculture, is projected to double by 2030.     

A Computational Approach Based on GIS Technology for the Development of an Anthropogenic Emission Inventory of Gaseous Pollutants in Greece

This paper describes a computational system developed for the compilation of an anthropogenic emission inventory of gaseous pollutants for Greece. The inventory was developed using a geographical information system integrated with SQL programming language to provide high temporal gridded emission fields for CO, NO₂, NO, SO₂, NH₃ and 23 non-methane volatile organic compounds (NMVOCs) species for the reference year 2003. Activity and statistical data from national sources were used for the quantification of emissions from the road transport, the other mobile sources and machinery sectors and from range activities using top-down or bottom-up methodologies. Annual emission data from existing national and European emission databases were also used. The emission data were spatially and temporally disaggregated using source-specific spatiotemporal indicators. On national scale, the road transport sector produces about 60% of the annual CO and NMVOC total emissions, with gasoline vehicles being the main CO and NMVOC emissions source. The road transport is responsible for approximately half of the higher alkanes and for more than half of the ethene and toluene emissions. The maritime sector accounts for about 40% of the annual total NO_x emissions, most of which are emitted by the international shipping subsector, whilst SO₂ is emitted mainly by the energy sector. The evaluation of the emissions inventory suggests that it provides a good representation of the amounts of gaseous pollutants emitted on national scale and a good characterisation of the relative composition of CO and NO_x emission in the large urban centres.     

Precipitation Composition in the Ohio River Valley: Spatial Variability and Temporal Trends

Sulfate (SO₄ ^2?), nitrate (NO₃ ^?) and ammonium (NH₄ ⁺) concentrations in precipitation as measured at NADP sites within the Ohio River Valley of the Midwestern USA between 1985 and 2002 are quantified and temporal trends attributed to changes/ variations in (i) the precipitation regime, (ii) emission patterns and (iii) air mass trajectories. The results indicate that mean SO₄ ^2? concentrations in precipitation declined by 37–43% between 1985 and 2002, while NO₃ ^? concentrations decreased by 1–32%, and NH₄ ⁺ concentrations exhibited declining concentrations at some sites and increasing concentrations at others. The change in SO₄ ^2? concentrations is in broad agreement with estimated reductions in sulfur dioxide emissions. Changes in NO₃ ^? concentrations appear to be less closely related to variations in emissions of oxides of nitrogen and exhibit a stronger dependence on weekly precipitation volume. Up to one quarter of the variability in log-transformed weekly NO₃ ^? concentrations in precipitation is explicable by variations in precipitation volume. Trends in annual average log-transformed SO₄ ^2? concentrations exhibit only a relatively small influence of variability in weekly precipitation amount but at each of the sites considered the variance explanation of annual average log-transformed SO₄ ^2? by sampling year was increased by removing the influence of precipitation volume. Annual mean log-transformed ion concentrations detrended for precipitation volume (by week) and emission changes (by year) exhibit positive correlations at all sites, indicating that the residual variability of SO₄ ^2?, NO₃ ^? and NH₄ ⁺ may have a common source which is postulated to be linked to synoptic scale variability and air mass trajectories.     

A Module to Calculate Primary Particulate Matter Emissions and Abatement Measures in Europe

Primary particulate matter is emitted directly into the atmosphere from various anthropogenic and natural sources such as power plants (combustion of fossil fuels) or forest fires. Secondary particles are formed by transformation of SO₂, NO_x, NH₃, and VOC in the atmosphere. They both contribute to ambient particulate matter concentrations, which may have adverse effects on human health. Health hazards are caused by small particulate size, high number of especially fine (< 2.5 µm) and ultra-fine (< 0.1 µm) particles and/or their chemical composition. As part of an integrated assessment model developed at IIASA, a module on primary particulate matter (PM) emissions has been added to the existing SO₂, NO_x, NH₃ and VOC sections. The module considers so far primary emissions of total suspended particles (TSP), PM₁₀ and PM_2.5 from aggregated stationary and mobile sources. A primary PM emission database has been established. Country specific emission factors for stationary sources have been calculated within the module using the ash content of solid fuels.     

The role of nitrogen oxides in oxidant production as predicted by the Regional Acid Deposition Model (RADM)

Regional oxidant distributions produced under various atmospheric conditions and emission scenarios are investigated using the Regional Acid Deposition Model (RADM). RADM is a complex, evolving three-dimensional Eulerian model that describes the chemistry, transport and deposition of tropospheric trace species including SO₂, sulfate, NO _x and volatile organic compounds as well as O₃, other major oxidants and acids. The model calculates the short-term temporal evolution of atmospheric trace gas concentrations and their deposition on the regional scale. This study is focused on oxidant production in the eastern United States and southeastern Canada. The influence of atmospheric conditions is explored by comparing three characteristic winter, summer and spring/fall cases. Base-case 1985 emissions of SO _x , NO _x , volatile organic compounds (VOCs), NH₃ and CO are specified using the comprehensive pollutant emissions inventory developed as part of the National Acid Precipitation Assessment Program (NAPAP). The perturbed case, which represents projected anthropogenic emission changes for 2010, indicates changes in daily total 80 km grid average NO _x emissions ranging from increases of 75% to decreases of 45% and VOC emission changes ranging from increases of 65% to decreases of 20%. The largest NO _x emission changes occur in the northeast, and the largest VOC changes occur in the Gulf Coast area. Ground level grid average midday O₃ concentrations for the 1985 emission cases are highest (on the order of 70 to 100 ppb) in the New York City and Houston metropolitan areas for the summer and spring cases; the summer case also indicates relatively high grid average O₃ concentrations of greater than 80 ppb in the southeast. Winter case values are much lower than summer O₃ values throughout the region, with highs of 40 to 50 ppb occurring in the southeast and the Great Lakes area. Changes in NO _x and other emissions under the complex 2010 emissions scenario for the summer case result in maximum O₃ concentration reductions of 10% in the Houston area and increases in O₃ of a few percent in some rural areas of the southeast. This study underscores the need for more comprehensive assessment of the complex relationships among regional emission changes, oxidant production and atmospheric conditions.     

Acid deposition to nature areas in the Netherlands: Part I. Methods and results

In this paper estimates of dry and wet deposition of acidifying substances in the Netherlands are presented. The deposition was estimated from measured concentrations in the atmosphere and in precipitation or if these were not available, from modelled concentrations. The method was applied for the Netherlands on a 5×5 km scale. The most important components are sulphur oxides and ammonia and their reaction products. It was estimated that the annual average deposition of SO _x in the Netherlands decreased from 1570 to 670 mol ha^?1 a^?1 between 1980 and 1989. In 1989, the annual average NO _y deposition was estimated to be 1220 mol ha^?1 a^?1 in 1980 and 1160 mol ha^?1 a^?1 in 1989. The annual average NH _x deposition in the Netherlands was estimated to be 2330 and 2190 mol ha^?1 a^?1 in 1980 and 1989 respectively. HCI deposition was about 100 mol ha^?1 a^?1 in all years. Dry deposition contributes most to the total deposition for each component. The spatial distribution of the total deposition shows a gradient over the Netherlands with highest values in the South and lowest in the North of the country. Meteorological conditions are also of influence on the deposition fluxes for all components. During 1988 and 1989 meteorological conditions favoured low deposition. The estimated uncertainty in the average fluxes of SO _x , NO _y , and NH _x for the Netherlands is 15, 25, and 30% respectively. The wet deposition fluxes can be estimated more accurately than the dry deposition.     

Estimation of source-receptor matrices for deposition of NOx-N

The contributions of the anthropogenic sources of NO_x from various combinations of contiguous U.S. states or Canadian provinces to integrated deposition across selected states or provinces are estimated with the Advanced Statistical Trajectory Regional Air Pollution (ASTRAP) model. The model assumes linearity between emissions and deposition, and uses the same parameterization methods, although with different rates, as in simulations of transport and deposition of SO_X. Vertical distributions of emissions for the two classes of pollutants are substantially different in the gridded inventories used in simulations, with a weighted mean effective emission height of 160 m for NO_X and 310 m for SO_X. This might be expected to lead to an effective transport distance before deposition shorter for NO_X than for SO_X. However, the calculated fraction of NO_X emissions deposited within the contiguous United States and Canada south of 60 deg N (57%) is not greatly different from the fraction calculated for SOX emissions (54%). This suggests that there may be compensating factors in the horizontal distribution of NO_X emissions, and in the lower dry deposition velocities for NO/NO₂ than for SO₂ in ASTRAP.     

An analysis of spatial variability of the dominant ions in precipitation in the eastern United States

Data of the Multistate Atmospheric Power Production Pollution Study (MAP3S) and the National Atmospheric Deposition Program (NADP) were utilized to develop wet deposition spatial distribution patterns for the eastern United States for 1979. The ions of SO₄ ^?, NO₃ ^?, H⁺, and NH₄ ⁺ were selected for study since they are the most prominent ones found in precipitation. Total wet deposition for 1979 was normalized to one centimeter of precipitation and objectively analyzed using the Synagraphic Mapping System (SYMAP) technique. Gradients of SO₄ ^? and NO₃ ^? were found to be essentially uniform, both to the east and west of the major pollution regions. An increased gradient in normalized deposition for SO₄ ^?, NO₃ ^?, and H⁺ was found in the Appalachian Mountain region. Estimates of total wet deposition were obtained by using the normalized deposition values in conjunction with precipitation as reported by the National Climatic Center. SYMAP analyses of the estimated total wet deposition were localized in nature due to precipitation variations between sites.     

Summertime study of acid deposition in the Detroit area

A comprehensive acid-deposition measuring station has been set up at the General Motors Technical Center site in Warren, Michigan. A second station is also being operated at a rural site near Lapeer, Michigan, which is approximately 54 km north of the Warren site. This report presents the results of this study for the June-September 1981 period. The rain composition was similar at both sites with the pH averaging 4.1 and the SO₄ ⁼/NO₃ ^? equivalence ratio averaging 2.1:1. This similarity suggests that local sources, i.e., relatively high emissions near the Warren site, and low emissions near the Lapeer site, have little effect on rain composition. The SO₄ ⁼/NO₃ ^? ratio for individual rain events in Warren reflected the SO₂/NO_x emission ratio in the area from which the event had come. Thus, the highest SO₄ ⁼/NO₃ ^? ratios were observed for rains that arrived from the southeast and the lowest ratios for rains from the southwest. No rain events arrived from a northwesterly direction during this sampling period. Measurements were carried out at both sites to estimate the relative contribution of dry deposition. The ambient particulate was acidic about half the time and basic half the time. The acidity in the particulate was due to acid SO₄ ⁼ and the basicity was due to soil-related materials. Gaseous HNO₃ averaged 2.0 μg m^?3while the basic gas, NH₃, averaged 0.83 μg m^?3. Based on these measurements, it was estimated that dry deposition of particles and HNO₃ contributed less than 10% of the total deposition of acidity during this study period.     

An Integrated Assessment Model for Fine Particulate Matter in Europe

Exposure to fine particles in the ambient air is recognized as a significant threat to human health. Two pathways contribute to the particle burden in the atmosphere: Fine particles originate from primary emissions, and secondary organic and inorganic particles are formed from the gas phase from the emissions of 'conventional' pollutants such as SO₂, NO_x, VOC and NH₃. Both types of particulate matter can be transported over long distances in the atmosphere. An integrated assessment model for particulate matter developed at IIASA addresses the relative importance of the different types of particulates, distinguishing primary and secondary particles and two size fractions. The model projects these emissions into the future and seeks cost-effective strategies for reducing health risks to population. The model integrates the control of primary emissions of fine particles with strategies to reduce the precursor emissions for the secondary aerosols. Preliminary results addressing the PM_2.5 fraction of both primary and secondary particulate matter indicate that in Europe the exposure to particulates will be significantly reduced as a side effect of the emission controls for conventional air pollutants (SO₂, NO_x, NH₃).     

Approaching Cumulative Effects through Air Pollution Modelling

The research presented here represents a segment of a cumulative impact assessment of resource development in northeastern British Columbia. It considers point and area source emissions of sulphur and nitrogen oxides (SO₂ and NO _x , respectively), over a 2,156-km² area. With the exception of open burning, all emissions are from Upstream Oil and Gas (UOG) sector sources (SO₂, n?=?103; NO _x , n?=?250; area, n?=?25). AERMOD View? was used to estimate the maximum potential concentration and deposition of these pollutants over 1-h, 3-h, 24-h, and annual averaging periods. Results are compared with various thresholds and limits from the policy and scientific literature to assess the potential cumulative effects of these pollutants. Of the thresholds employed, exceedances of the 1-h and 24-h NO _x concentrations and the annual SO₂ concentration are predicted. There were no predicted exceedances of annual deposition thresholds (i.e., ??Critical Loads??). Maximum predicted concentrations vary between compounds and are related to boundary layer stability, elevation, and distance from sources. Comparison with nearby monitoring data indicated that predicted concentrations were reasonable and that AERMOD provides a useful tool for approaching the potential cumulative impacts of air pollution from multiple sources. While the accuracy of Gaussian-based annual deposition estimates is questioned, model enhancements that could extend the application to more comprehensive assessments are suggested. Lastly, the implications of predicted threshold violations for forest ecosystems and local forest-dependent First Nations communities are discussed.     

Nature and Magnitude of Atmospheric Fluxes of Total Inorganic Nitrogen and Other Inorganic Species to the Tampa Bay Watershed, FL, USA

We estimated the total inorganic fluxes of nitrogen (N), sulfur (S), chloride (Cl^?, sodium (Na⁺, calcium (Ca²⁺, magnesium (Mg²⁺, potassium (K⁺ and hydronium (H⁺. The resistance deposition algorithm that is programmed as part of the CALMET/CALPUFF modeling system was used to generate spatially-distributed deposition velocities, which were then combined with measurements of urban and rural concentrations of gas and particle species to obtain dry deposition rates. Wet deposition rates for each species were determined from rainfall concentrations and amounts available from the National Acid Deposition Program (NADP) monitoring network databases. The estimated total inorganic nitrogen deposition to the Tampa Bay watershed (excluding Tampa Bay) was 17 kg-N ha^?1 yr^?1 or 9,700 metric tons yr^?1, and the ratio of dry to wet deposition rates was ～2.3 for inorganic nitrogen. The largest contributors to the total N flux were ammonia (NH₃ and nitrogen oxides (NO _x at 4.6 kg-N ha^?1 yr^?1 and 5.1 kg-N ha^?1 yr^?1, respectively. Averaged wet deposition rates were 2.3 and 2.7 kg-N ha^?1 yr^?1 for NH₄ ⁺ and NO₃ ^?, respectively.     

Estimation of Dry Deposition by Using a Filter Pack Method at Chunchon, Korea

Atmospheric gases and particulates were collected using four-stage filter-pack in Chunchon from January through December in 1999. Particulate SO₄ ^2? and NO₃ ^?, and gaseous HNO₃, SO₂ and NH₃ were analyzed. Annual average concentration of SO₄ ^2?(S), NO₃ ^?(S), HNO₃ (g), SO₂(g) and NH₃(g) were 5.75µg/m³, 4.98µg/m³, 0.33ppb, 1.52ppb and 7.25ppb, respectively. Annual dry deposition fluxes were estimated using the measured concentration and dry deposition velocity published by other research group. Annual dry deposition of S was 287kg · (km)^?2·y^?1, which accounted for about 30% of total S deposition. For N deposition, dry deposition is predominant; about 70% of total N deposition was through dry process mostly as forms of NH₃ and HNO₃.     

Trends in Emissions of Acidifying Species in Asia, 1985–1997

Acid deposition is a serious problem throughout much of Asia. Emissions of sulfur dioxide (SO₂) and nitrogen oxides (NO_x) have been increasing steadily, as nations strive to increase their levels of economic development. Coal and fuel oil have been the main choices for powering industrial development; and, until recently, only a few countries had taken steps to avert the atmospheric emissions that accompany fuel combustion. This paper discusses trends in emissions of SO₂ and NO_x that have occurred in Asian countries in the period 1985–1997, using results from the RAINS-Asia computer model and energy-use trends from the IEA Energy Statistics and Balances database. Emissions of SO₂ in Asia grew from 26.6 Tg in 1985 to 33.7 Tg in 1990 and 39.2 Tg in 1997. Though SO₂ emissions used to grow as fast as fossil-fuel use, recent limitations on the sulfur content of coal and oil have slowed the growth. The annual-average emissions growth between 1990 and 1997 was only 2.2%, considerably less than the economic growth rate. Emissions of NO_x, on the other hand, continue to grow rapidly, from 14.1 Tg in 1985 to 18.7 Tg in 1990 and 28.5 Tg in 1997 (6.2% per year between 1990 and 1997), with no signs of abating. Thus, though SO₂ remains the major contributor to acidifying emissions in Asia, the role of NO_x will become more and more important in the future.     

Simultaneous Determination of Gas and Particle Dry Deposition onto Conditioned Surrogate Surfaces

Aerodynamically designed surrogate surfaces were used to determine the relative importance of gaseous (SO₂, HNO₃, NH₃) and particulate species (SO₄ ^2?, NO₃ ^?, NH₄ ⁺, Ca²⁺) in the dry deposition flux. For 11 sampling periods, we measured the deposition fluxes, ambient gaseous concentrations, size distributions of atmospheric aerosols and some meteorological parameters in Uji. The dry deposition of the gas to a nearly perfect sink was calculated by subtracting the greased surface flux from the total deposition flux to both the greased and reagent impregnated (or water) surface. It was found that the gas phase deposition contributed significantly more (60–93%) than the particulate phase to overall deposition of sulfur and nitrogen compounds. The dry deposition velocities of the species were also calculated using the deposition fluxes and the measured ambient concentrations. Comparisons were made between the measured and modeled particulate deposition flux.     

Nitrogen Deposition and Strategies for the Control of Acidification and Eutrophication across Great Britain

It is now recognised that a multi-pollutant, multi-effect approach needsto be adopted to address the range of problems caused by atmosphericpollution. In this paper we use a relatively simple trajectory model (HARM)to explore the coupled behaviour of sulphur dioxide (SO₂),oxides of nitrogen (NO_x) and ammonia (NH₃) andthe possible effects of future reductions in emissions of these pollutantson depositions of S and N across Great Britain. The performance of HARM withrespect to concentrations and depositions of NO_y andNH_x is assessed by comparison with data from nationalmonitoring networks. A range of emissions scenarios are modelled and theeffects of these reductions on critical loads exceedance are explored usingthe critical loads function (CLF), which allows both the acidification andeutrophication effects of S and N deposition to be explored simultaneously.Spatial variations in the reductions of deposition of S and/or N required tomeet critical loads are described. Reductions in emissions of the precursorsof strong acids (SO₂ and NO_x) yield benefits interms of ammonium deposition as a result of their coupled chemistry. Thedevelopment of strategies to control nitrogen deposition will need to take this non-linearity in to account.     

Fluxes and Trends of Nitrogen and Sulphur Compounds at Integrated Monitoring Sites in Europe

The International Cooperative Programme on Integrated Monitoring (ICP IM) is part of the effects monitoring strategy of the UN/ECE Convention on Long-Range Transboundary Air Pollution. We calculated input-output budgets and trends of N and S compounds, base cations and hydrogen ions for 22 forested ICP IM catchments/plots across Europe. The site-specific trends were calculated for deposition and runoff water fluxes and concentrations using monthly data and non-parametric methods. The reduction in deposition of S and N compounds, caused by the new Gothenburg Protocol of the Convention, was estimated for the year 2010 using atmospheric transfer matrices and official emissions. Statistically significant downward trends of SO₄, NO₃ and NH₄ bulk deposition (fluxes or concentrations) were observed at 50% of the ICP IM sites. Implementation of the new UN/ECE emission reduction protocol will further decrease the deposition of S and N at the ICP IM sites in western and northwestern parts of Europe. Sites with higher N deposition and lower C/N-ratios clearly showed an increased risk of elevated N leaching. Decreasing SO₄ and base cation trends in output fluxes and/or concentrations of surface/soil water were commonly observed at the ICP IM sites. At several sites in Nordic countries decreasing NO₃ and H⁺ trends (increasing pH) were also observed. These results partly confirm the effective implementation of emission reduction policy in Europe. However, clear responses were not observed at all sites, showing that recovery at many sensitive sites can be slow and that the response at individual sites may vary greatly.     

Acidifying emissions in The Netherlands

The emission of acidifying compounds to air in the Netherlands, expressed as acidifying equivalents, consisted in 1992 mainly of NO_X (45%), NH₃ (35%) and SO₂ (20%). Transportation, agriculture and large combustion plants each contributed about 30% to the national total emission of acidifying compounds. The emissions from transportation activities mainly consisted of NO_X, while in agriculture NH₃ emission strongly dominated. Combustion processes in large combustion plants resulted both in SO₂ emissions (especially from refineries) and NO_X emissions (especially from public power plants). The total emission of acidifying substances decreases steadily in the Netherlands. The emission in 1992 was 24% lower than in 1985. It is expected to decrease further in future. The emission levels in 1992 and 1993 still are more than twice as high as the emission objective for the year 2000, set by Dutch environmental policy.     

Atmospheric Deposition of Acidifying Components to a Japanese Cedar Forest

One-year field measurements were conducted in a Japanese cedar (Cryptomeria japonica) forest, located in Gunma Prefecture, Japan. On the basis of the meteorological and atmospheric concentration data, the dry deposition of SO₂, HNO₃, NO₂ and HCl was estimated using the inferential method. The annual dry deposition of H⁺ was estimated at 721 eq ha^?1yr^?1, which was 40% larger than the measured annual wet deposition of H⁺ (514 eq ha^?1yr^?1). Therefore, dry deposition is an important pathway for the atmospheric input of H⁺ to the forest in the study site. The contribution of each gas to the dry deposition of H⁺ was as follows: SO₂, 25%; HNO₃, 32%; NO₂, 10%; and HCl, 33%. The extremely high contribution of HCl appeared to be caused by the high emission intensity of HCl due to waste incineration in the site region. The differences between estimated deposition and throughfall and stemflow measurements indicated that about 80% of the total deposition of H⁺ was taken up by the canopy.