Nonlinearities in source receptor relationships for sulfur and nitrogen compounds

The relationship between emissions and deposition of air pollutants, both spatially and in time forms an important focus for science and for policy makers. In practice, this relationship may become nonlinear if the underlying processes change with time, or in space. Nonlinearities may also appear due to errors in emission or deposition data, and careful scrutiny of both data sources and their relationship provides a means of picking up such deficiencies. Nonlinearities in source receptor relationships for sulfur and nitrogen compounds in Europe have been identified in measurement data for the UK. In the case of sulfur, the dry deposition process has been shown to be strongly influenced by ambient concentrations of NH3, leading to substantial increases in deposition rate as SO2 concentrations decline and the ratio SO2/NH3 decreases. The field evidence extends to measurements over three different surfaces in three countries across Europe. A mechanistic understanding of the cause of this nonlinearity has been provided. Apparent nonlinearities also exist in the sulfur deposition field through the influence of shipping emissions. The effect is clear at west coast locations, where during a period in which land-based sulfur emissions declined by 50%, no significant decline in concentrations of SO(2-) in precipitation were observed. The sites affected are primarily the coastal regions of southwestern UK, where shipping sources contribute a substantial fraction of the deposited sulfur, but the effect is not detectable elsewhere. Full quantification of the spatially disaggregated emission and their changes in time will eliminate this apparent nonlinearity in the source-receptor data. For oxidized nitrogen emission and deposition in the UK, there is strong evidence of nonlinearity in the source-receptor relationship. The concentrations and deposition of NO(3-) in precipitation have declined little following a reduction in emissions of 45% during the period 1987 to 2001. The data imply a significant decrease in the average transport distance for oxidized nitrogen and most probably an increase in the average oxidation rate. However, the net effect of changes in aerosol chemistry due to changes in sulfur emissions and less competition for the main oxidants as a consequence of reductions in sulfur emission have not been separated. A quantitative explanation of the cause of this nonlinearity is lacking and the effects are therefore identified as an important uncertainty for the development of further protocols to control acidification, eutrophication and photochemical oxidants in Europe.     

The contribution of ammonia emissions from agriculture to the deposition of acidifying and eutrophying compounds onto forests

In the vicinity of a large ammonia emission area, dry and wet deposition of acidifying and eutrophying compounds onto Douglas Fir forests was studied by sampling throughfall, stemflow and bulk precipitation. Deposition amounts of NH(4)(+) and SO(4)(2-) were recognised to be among the highest of Central Europe, resulting in extremely high inputs of (potential) acid to the forest soils (13.1 kEq ha(-1) year(-1)). The contribution of NH(3) emissions from agriculture to the total acid deposition to the forests was 52%. The total nitrogen deposition amounted to 115.0 kg ha(-1) year(-1), 83% originating from NH(3) emissions and 17% from NO(x) emissions. Calculated mean dry deposition velocities of NH(3) and SO(2) were much larger than reported in the literature. A synergistic effect between NH(3) and SO(2) in the process of dry deposition is suggested and evidence for this effect is discussed. When deposition models do not take this interaction into account, they will underestimate NH(3) and SO(2) deposition amounts in areas with intensive animal husbandry.     

Modelling the spatial distribution of SO2 and NOx emissions in Ireland

The spatial distributions of sulphur dioxide (SO2) and nitrogen oxides (NOx) emissions are essential inputs to models of atmospheric transport and deposition. Information of this type is required for international negotiations on emission reduction through the critical load approach. High-resolution emission maps for the Republic of Ireland have been created using emission totals and a geographical information system, supported by surrogate statistics and landcover information. Data have been subsequently allocated to the EMEP 50 x 50-km grid, used in long-range transport models for the investigation of transboundary air pollution. Approximately two-thirds of SO2 emissions in Ireland emanate from two grid-squares. Over 50% of total SO2 emissions originate from one grid-square in the west of Ireland, where the largest point sources of SO2 are located. Approximately 15% of the total SO2 emissions originate from the grid-square containing Dublin. SO2 emission densities for the remaining areas are very low, < 1 t km-2 year-1 for most grid-squares. NOx emissions show a very similar distribution pattern. However, NOx emissions are more evenly spread over the country, as about 40% of total NOx emissions originate from road transport.     

Trends in atmospheric ammonium concentrations in relation to atmospheric sulfate and local agriculture

Ammonium (NH(4)(+)) concentrations in air and precipitation at the Institute of Ecosystem Studies (IES) in southeastern New York, USA declined over an 11-year period from 1988 to 1999, but increased from 1999 to 2001. These trends in particulate NH(4)(+) correlated well with trends in particulate SO(4)(2-) over the 1988-2001 period. The NH(4)(+) trends were not as well correlated with local cattle and milk production, which declined continuously throughout the period. This suggests that regional transport of SO(4)(2-) may have a greater impact on concentrations of NH(4)(+) and subsequent deposition than local agricultural emissions of NH(3). Ammonium concentrations in precipitation correlated significantly with precipitation SO(4)(2-) concentrations for the 1984-2001 period although NH(4)(+) in precipitation increased after 1999 and SO(4)(2-) in precipitation continued to decline after 1999. The correlation between NH(4)(+) and SO(4)(2-) was stronger for particulates than for precipitation. Particulate NH(4)(+) concentrations were also correlated with particulate SO(4)(2-) concentrations at 31 of 35 eastern U.S. CASTNet sites that had at least 10 years of data. Air concentrations of NH(4)(+) and SO(4)(2-) were more strongly correlated at the sites that were located within an agricultural landscape than in forested sites. At most of the sites there was either no trend or a decrease in NH(4)(+) dry deposition during the 1988-2001 period. The sites that showed an increasing trend in NH(4)(+) dry deposition were generally located in the southeastern U.S. The results of this study suggest that, in the northeastern U.S., air concentrations of NH(4)(+) and subsequent deposition may be more closely linked to SO(4)(2-) and thus SO(2) emissions than with NH(3) emissions. These results also suggest that reductions in S emissions have reduced NH(4)(+) transport to and NH(4)(+)-N deposition in the Northeast.     

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.     

A simple model which predicts some non-linear features between atmospheric sulphur and sulphur emissions

This paper develops a simple model and suggests a plausible chemico-physical mechanism for a non-linear response between atmospheric sulphur and sulphur emissions. It contains simplified representations of transport, deposition and conversion processes and uses a proxy in-cloud oxidant-limited reaction along a pathway connecting an emission source with a receptor site. Individual pathway responses to emissions show linear behaviour above a threshold. However, by averaging the values of SO2 at the receptor site from different pathways a continuous non-linear relationship is obtained. As emissions reduce, distant emission sources become less significant contributors of sulphur dioxide at a receptor site but their emissions are still counted in an emission inventory, leading to an apparent non-linearity. Sulphate is always found to contribute a signal to the receptor site total. This model goes someway to explaining a proposed 'crossover' between observed proportions of wet and dry deposited sulphur in the UK as emissions have been reduced.     

Errors in representing regional acid deposition with spatially sparse monitoring: Case studies of the eastern US using model predictions

The current study uses case studies of model-predicted regional precipitation and wet ion deposition over 5-year periods to estimate errors in corresponding regional values derived from the means of site-specific values within regions of interest located in the eastern US. The mean of model-predicted site-specific values for sites within each region was found generally to overestimate the corresponding model-predicted regional wet ion deposition. On an annual basis across four regions in the eastern US, these overestimates of regional wet ion deposition were typically between 5 and 25% and may be more exaggerated for individual seasons. Corresponding overestimates of regional precipitation were typically <5%, but may be more exaggerated for individual seasons. Period-to-period relative changes determined from the mean of site-based model-predicted wet deposition for the current regional ensembles of sites generally estimated larger beneficial effects of pollutant emissions reductions in comparison to changes based on model-predicted regional wet deposition. On an annual basis site-based relative changes were generally biased low compared to regional relative changes: differences were typically <7%, but they may also be more exaggerated for individual seasons. Spatial heterogeneities of the wet ion deposition fields with respect to the sparse monitoring site locations prevented the monitoring sites considered in the current study from providing regionally representative results. Monitoring site locations considered in the current study over-represent the geographical areas subject to both high emissions and high wet ion deposition and under-represent the geographical areas subject to low emissions and low wet deposition. Since the current case studies consider only those eastern US site locations that have supported concurrent wet and dry deposition monitoring, similar errors may be expected for dry and total deposition using results from the same monitoring site locations. Current case study results illustrate the approximate range of potential errors and suggest caution when inferring regional acid deposition from a network of sparse monitoring sites.     

Response of drinking-water reservoir ecosystems to decreased acidic atmospheric deposition in SE Germany: trends of chemical reversal

This study evaluates chemical trends of seven acidified reservoirs and 22 tributaries in the Erzgebirge from 1993 to 2003. About 85% of these waters showed significantly (p < 0.05) declining concentrations of protons (-69%), nitrate (-41%), sulfate (-27%), and reactive aluminum (-50% on average). This reversal is attributed to the intense reduction of industrial SO2 and NOx emissions from formerly high levels, which declined by 99% and 82% in the German-Czech border region between 1993 and 1999. The deposition rates of protons and sulfur decreased by 70-90%. Since 1993, the dry deposition of total inorganic nitrogen diminished to a minor degree, but the wet deposition remained unchanged. The surface waters reflect a substantial decrease in Al exchange processes, a release of sulfur previously stored in soils, and an uptake of nitrate by forest vegetation. The latter effect may be supported by soil protection liming which contributed to the chemical reversal in almost 20% of the study waters.     

Atmospheric deposition and canopy exchange processes in heathland ecosystems

The aims of the present study were to determine canopy exchange processes and to quantify total atmospheric deposition of sulphur and nitrogen in heathland. The study was carried out in dry inland heath vegetation, dominated by Calluna vulgaris, in two nature reserves in the eastern part of the Netherlands. Atmospheric deposition was determined with throughfall-stemflow measurements, adapted for low vegetation. Throughflow measurements (sum of throughfall and stemflow) in artificial Calluna canopies showed co-deposition of SOx and NHy upon heathland vegetation. In the real Calluna canopy, a significant part of the deposited ammonia/ammonium was directly assimilated by the Calluna shoots, especially in wet periods. The concentrations of potassium, calcium and magnesium in throughflow, after passage through the Calluna canopy, increased significantly compared with bulk precipitation. The amount of cations lost from the canopy were in good agreement with the observed ammonium uptake by the Calluna. A field experiment demonstrated that losses of the above-mentioned cations can be doubled by application of ammonium sulphate. It was shown that interception deposition is an important component of the atmospheric deposition of sulphur and nitrogen upon Calluna heathland; bulk precipitation amounted to only c. 35-40% of total atmospheric input. Total atmospheric deposition of sulphur and nitrogen in the investigated heathlands was 1.5-2.1 (27-33 kg S ha(-1) yr(-1)) and 2.1-3.1 kmolc ha(-1) yr(-1) (30-45 kg N ha(-1) yr(-1)), respectively. It is concluded that the present atmospheric nitrogen deposition is a continuous threat for the existence of heathlands in Western Europe.     

Long-term relationships between mercury wet deposition and meteorology

Daily-event precipitation samples collected in Underhill, VT from 1995 to 2006 were analyzed for total mercury and results suggest that there were no statistically significant changes in annual mercury wet deposition over time, despite significant emissions reductions in the Northeast United States. Meteorological analysis indicates that mercury deposition has not decreased as transport of emissions from major source regions in the Midwest and East Coast have consistently contributed to the largest observed mercury wet deposition amounts over the period. In contrast, annual volume-weighted mean (VWM) mercury concentration declined slightly over the 12-years, and a significant decrease was observed from CY 2001 to 2006. An increase in the total annual precipitation amount corresponded with the decline in annual VWM mercury concentration. Analysis suggests that the increase in precipitation observed was strongly related to changes in the amount and type of precipitation that fell seasonally, and this departure was attributed to a response in meteorological conditions to climate variability and the El Niño-Southern Oscillation (ENSO) cycle. Increased amounts of rainfall and mixed precipitation (mixture of rainfall and snowfall), particularly in the spring and fall seasons, enhanced annual precipitation amounts and resulted in declining VWM mercury concentrations during these periods. Thus, declines in concentration at the more remote Underhill site appear to be more directly linked to local scale meteorological and climatological variability than to a reduction in emissions of mercury to the atmosphere.     

The effect of the limited availability of H2O2 in the competitive deposition of sulfur and oxidized nitrogen

To understand the influence of the reduction of SO2 emissions from a single source in the S and N deposition around its local environment, the application of the Sulphur Transport Eulerian Model 2 (STEM-II) was introduced in this paper. Observed local deposition patterns were analysed and explained in terms of the main processes involved in the pollutants deposition. It was necessary to take into account the limited availability of H2O2 because of its influence on both S(IV) and oxidized nitrogen deposition. In order to estimate the quantitative relationship between the SO2 emissions reduction and the observed S and N deposition patterns, these processes were simulated for different meteorological conditions. Simulation results were in agreement with both observed deposition patterns and limited availability of H2O2, specially if significant changes in the S deposition patterns were considered. Both observed and estimated S deposition patterns changed their top value location from the Southwest (1990) to the Northwest (1997) of the domain, because of the reduction of dry deposition. The global reduction of total S depositions, estimated and observed, were in good agreement too. Model simulations could explain the higher S dry deposition reduction, considering the emissions reduction strategy applied.     

Sulphur and seasalt deposition as reflected by throughfall and runoff chemistry in forested catchments

At forested catchments at Lake G?rdsj?n on the Swedish west coast the deposition and runoff chemistry has been followed during the period 1979-1990 by throughfall and runoff measurements as well as by measurements of atmospheric concentrations. The 10-year means in throughfall and runoff are very similar for sulphur and the main seasalt ions sodium and chloride; for sulphur 26.1 and 27.6 kg ha(-1) yr(-1), for sodium 49 and 52 kg ha(-1) yr(-1) and for chloride 96 kg ha(-1) yr(-1) and 93 kg ha(-1) yr(-1), respectively. The actual flows are 100-200% higher than the wet deposition as collected in open bulk precipitation collectors indicating a very large input by dry deposition. One important question is to what extent the throughfall and runoff values can be used as measures of total deposition. We present results from studies at different experimental catchments illustrating the possibilities of using throughfall and runoff data as measures of atmospheric deposition of sulphur and seasalt.     

Atmospheric nitrogen deposition in south-east Scotland: Quantification of the organic nitrogen fraction in wet,dry and bulk deposition

Water soluble organic nitrogen (WSON) compounds are ubiquitous in precipitation and in the planetary boundary layer, and therefore are a potential source of bioavailable reactive nitrogen. This paper examines weekly rain data over a period of 22 months from June 2005 to March 2007 collected in 2 types of rain collector (bulk deposition and “dry + wet” deposition) located in a semi-rural area 15 km southwest of Edinburgh, UK (N55°51′44″, W3°12′19″). Bulk deposition collectors are denoted in this paper as “standard rain gauges”, and they are the design used in the UK national network for monitoring precipitation composition. “Dry + wet” deposition collectors are flushing rain gauges and they are equipped with a rain detector (conductivity array), a spray nozzle, a 2-way valve and two independent bottles to collect funnel washings (dry deposition) and true wet deposition. On average, for the 27 weekly samples with 3 valid replicates for the 2 types of collectors, dissolved organic nitrogen (DON) represented 23% of the total dissolved nitrogen (TDN) in bulk deposition. Dry deposition of particles and gas on the funnel surface, rather than rain, contributed over half of all N-containing species (inorganic and organic). Some discrepancies were found between bulk rain gauges and flushing rain gauges, for deposition of both TDN and DON, suggesting biological conversion and loss of inorganic N in the flushing samplers.     

Trends in atmospheric reactive nitrogen for the Eastern United States

Reactive nitrogen can travel far from emission sources and impact sensitive ecosystems. From 2002 to 2006, policy actions have led to decreases in NO(x) emissions from power plants and motor vehicles. In this study, atmospheric chemical transport modeling demonstrates that these emissions reductions have led to a downward trend in ambient measurements of transported reactive nitrogen, especially atmospheric concentrations and wet deposition of nitrate. The trend in reduced nitrogen, namely ammonium, is ambiguous. As reduced nitrogen becomes a larger fraction of the reactive nitrogen budget, wide-spread NH(3) measurements and improved NH(3) emissions assessments are a critical need.     

Past and future trends in concentrations of sulphur and nitrogen compounds in the Arctic

Recent trends in nitrogen and sulphur compounds in air and precipitation from a range of Arctic monitoring stations are presented, with seasonal data from the late 70s to 2004 or 2005. Earlier findings of declining sulphur concentrations are confirmed for most stations, while the pattern is less clear for reduced and oxidized nitrogen. In fact there are positive trends for nitrogen compounds in air at several stations. Acidity is generally reduced at many stations while the precipitation amount is either increasing or stable. Variability of sulphate concentrations in air for the period 1991–2000 is reasonably well reproduced at most stations using an Eulerian, hemispherical model. Results for nitrogen compounds are weaker. Scenario studies show that even if large sulphur emission reductions take place in important source regions in South-East Asia in the coming decades, only small changes in Arctic deposition can be expected. This is because South-East Asian emissions have small influence north of the Arctic circle.     

Satellite observations of the seasonal cycles of absorbing aerosols in Africa related to the monsoon rainfall, 1995–2008

The link between the African Monsoon systems and aerosol loading in Africa is studied using multi-year satellite observations of UV-absorbing aerosols and rain gauge measurements.The main aerosol types occurring over Africa are desert dust and biomass burning aerosols, which are UV-absorbing. The abundance of these aerosols over Africa is characterised in this paper using residues and Absorbing Aerosol Index (AAI) data from Global Ozone Monitoring Experiment (GOME) on board ERS-2 and SCanning Imaging Absorption SpectroMeter for Atmospheric ChartograpHY (SCIAMACHY) on board Envisat.Time series of regionally averaged residues from 1995 to 2008 show the seasonal variations of aerosols in Africa. Zonally averaged daily residues over Africa are related to monthly mean precipitation data and show monsoon-controlled atmospheric aerosol loadings. A distinction is made between the West African Monsoon (WAM) and the East African Monsoon (EAM), which have different dynamics, mainly due to the asymmetric distribution of land masses around the equator in the west. The seasonal variation of the aerosol distribution is clearly linked to the seasonal cycle of the monsoonal wet and dry periods in both studied areas.The residue distribution over Africa shows two distinct modes, one associated with dry periods and one with wet periods. During dry periods the residue varies freely, due to aerosol emissions from deserts and biomass burning events. During wet periods the residue depends linearly on the amount of precipitation, due to scavenging of aerosols and the prevention of aerosol emissions from the wet surface. This is most clear over east Africa, where the sources and sinks of atmospheric aerosols are controlled directly by the local climate, i.e. monsoonal precipitation. Here, the wet mode has a mean residue of ?1.4 and the dry mode has a mean residue of ?0.3. During the wet modes a reduction of one residue unit for every 160 mm monthly averaged precipitation was found. Shielding effects due to cloud cover may also play a role in the reduction of the residue during wet periods.A possible influence of aerosols on the monsoon, via aerosol direct and indirect effects, is plausible, but cannot directly be deduced from these data.     

Modelling the long-term soil response to atmospheric deposition at intensively monitored forest plots in Europe

The dynamic soil chemistry model SMART was applied to 121 intensive forest monitoring plots (mainly located in western and northern Europe) for which both element input (deposition) and element concentrations in the soil solution were available. After calibration of poorly known parameters, the model accurately simulated soil solution concentrations for most plots as indicated by goodness-of-fit measures, although some of the intra-annual variation especially in nitrate and aluminium concentrations could not be reproduced. Model evaluations of two emission-deposition scenarios (current legislation and maximum feasible reductions) for the period 1970-2030 show a strong reduction in sulphate concentrations between 1980 and 2000 in the soil due to the high reductions in sulphur emissions. However, current legislation hardly reduces future nitrogen concentrations, whereas maximum feasible reductions reduces them by more than half. Maximum feasible reductions are also more effective in increasing pH and reducing aluminium concentrations, mostly below ‘critical’ values.     

Indications for changing deposition patterns in central Europe

The German Federal Environmental Agency (Umweltbundesamt) currently runs a network of 17 air pollution monitoring stations in rural areas within the Federal Republic of Germany. Since 1982, daily bulk precipitation samples have been collected and analysed at five of these stations. As no changes in sampling and chemical analysis techniques have been introduced in this time period, an interpretation with respect to trends is possible. An increase in pH is most obvious at Deuselbach in the western part of Germany. It is related to a decrease in sulphate ions. Reduced SO2 emissions in the western part of Europe have resulted in decreasing ambient air concentrations mainly in the western part of Germany, whereas changes in concentrations close to the eastern border of West Germany were not as pronounced. Part of the decrease, however, was a consequence of three mild winters in sequence at the end of the period, with little easterly air flow. Estimated dry deposition fluxes of sulphur at 3 rural stations in West Germany were lower in 1988/1989 compared to 1980-1987 by 44-69%. Wet deposition showed between 8% increase and 25% decrease. The resulting reduction in total sulphur deposition ranged from 17-54%. Deposition via interception of fog droplets was not measured.     

Towards an assessment of the influence of climate on wet acidic deposition in Europe

The EMEP precipitation composition network is used to examine relationships between non-marine SO4(2-), NO3-, NH4+, H+ concentrations and precipitation amount and a local zonal pressure index (an index of the atmospheric circulation). The pattern of the relationships changes across Europe with the zonal pressure gradient explaining more of the variance in ion concentrations in the west, and precipitation amount explaining relatively more of the variance in the east. There is some predictive capability for precipitation composition in the zonal pressure gradient for restricted regions in Europe; R2 values are up to 40% on a daily basis but in some seasons/months attain >60%. The zonal pressure gradient is an index which appears to include pertinent information on transport and wet removal. Preliminary analysis indicates that this approach can be useful in assessing the contributions of changing atmospheric circulation to time-trends of wet acidic deposition in an area stretching from the UK over the North Sea to Denmark. The zonal pressure gradient is known to have varied on time-scales of decades, and the simple index may be one appropriate approach to assessing future deposition patterns from future climate projections.     

Sulphur dioxide adsorption in Scots pine canopies exposed to high ammonia emissions near a Cu-Ni smelter in SW Finland

Since 1994 the nickel-processing plant at the Cu-Ni smelter at Harjavalta, south-west Finland, has emitted considerable amounts of NH(3) into the atmosphere. The effects of NH(3) emissions on nitrogen and sulphur deposition in throughfall and the foliar nutrient status were investigated in a Scots pine stand at 0.5 km distance. Bulk deposition, stand throughfall and percolation water (20 cm depth) samples were collected at 4-week intervals during 1992-1998. pH and the Ca, Mg, K, NH(4) and SO(4) concentrations were determined on the samples. NH(3) emissions have strongly increased the scavenging of SO(2) from the air in the pine stand, and the increased levels of N and S deposition were clearly evident as increased foliar N and S concentrations and larger needle size. The increased input of SO(4) into the forest floor was not associated with an increase in the leaching of Ca and Mg from the surface soil layers.