Modelling Seasonal Dynamics from Temporal Variation in Agricultural Practices in the UK Ammonia Emission Inventory

Most ammonia (NH₃) emission inventories have been calculated on an annual basis and do not take into account the seasonal variability of emissions that occur as a consequence of climate and agricultural practices that change throughout the year. When used as input to atmospheric transport models to simulate concentration fields, these models therefore fail to capture seasonal variations in ammonia concentration and dry and wet deposition. In this study, seasonal NH₃ emissions from agriculture were modelled on a monthly basis for the year 2000, by incorporating temporal aspects of farming practice. These monthly emissions were then spatially distributed using the AENEID model (Atmospheric Emissions for National Environmental Impacts Determination). The monthly model took the temporal variation in the magnitude of the ammonia emissions, as well as the fine scale (1-km) spatial variation of those temporal changes into account to provide improved outputs at 5-km resolution. The resulting NH₃ emission maps showed a strong seasonal emission pattern, with the highest emissions during springtime (March and April) and the lowest emissions during summer (May to July). This emission pattern was mainly influenced by whether cattle were outside grazing or housed and by the application of manures and fertilizers to the land. When the modelled emissions were compared with measured NH₃ concentrations, the comparison suggested that the modelled emission trend corresponds fairly well with the seasonal trend in the measurements. The remaining discrepancies point to the need to develop functional parametrisations of the interactions with climatic seasonal variation.     

Measurement and Modelling of Ammonia Emissions at Waste Treatment Lagoon-Atmospheric Interface

Global emissions of ammonia are approximately 75 Tg N/yr (1 Tg =10¹²g). The major global source is excreta from domestic animals ( 32 Tg N ^-1yr^-1). Waste storage and treatment lagoonsare used to treat the excreta of hogs in North Carolina (NC). Proteins and nitrogen rich compounds in the lagoon are convertedto ammonia, through a series of biological and chemical transformations. The process of ammonia emission has been investigated using two different model approaches: (1) CoupledMass Transfer with Chemical Reaction Model (Model I), and (2)Mass Transport without Chemical Reaction Model (Model II). Asensitivity analysis is performed with the models, and the modelresults are compared with ammonia emission experiments at a swinewaste storage and treatment lagoon in NC using a dynamic emissionflux chamber.Results of model predictions of emission flux indicate an exponential increase in ammonia flux with increasing lagoontemperature and pH, a linear increase with increasing lagoontotal ammoniacal nitrogen (TAN), and a secondary degree increasewith the increasing wind speed. In addition, the fluxes predictedby Model I are consistently larger than fluxes predicted by Model II. Experimental values of flux agreed well with model predictions, with the experimental values lying in different positions between the two model predictions under different physical and chemical conditions. Further, when compared to diurnal and seasonal experimental flux values, Model I corroborates the results in calm meteorological conditions (windspeed U10 = 1.5 m s^-1). However, the observed results are better predicted by Model II during unstable conditions, when wind speeds are higher than 2.0 m s^-1 and physical transfer process functions dominate.     

Dynamics of Ammonia Exchange in Response to Cutting and Fertilising in an Intensively-Managed Grassland

Continuous micrometorological measurements of ammonia (NH₃)exchange were made for a period of 19 months (May 1998–November 1999) over intensively managed grassland in southern Scotland. This study focused on the influence of management activities, such as cutting and fertilising, on vegetation-atmosphere exchange of NH₃. Measurements were conducted within the European project GRAMINAE (GRassland AMmonia INteractions Across Europe) within which the Scottish site forms one of 6 sites in an E–W transect across Europe. NH₃ emissions were enhanced (up to 300 ng m^-2 s^-1) after cutting followed by larger emissions after fertilising (up to 1400 ng m^-2 s^-1). Annual budget calculations show the intensive grassland acted as a net source (1.8 kg N ha^-1 yr¹) although fluxes were bi-directional with deposition dominating in the winter and emission in the summer. Initial modelling of the NH₃ exchange using a `canopy compensation point' model has been conducted for key periods. The dynamics of the fluxes during these key periods, such as before and after cutting and fertilising, may be reproduced by introducing different values of the apoplastic ratio, = [NH₄ ⁺]/[H⁺].     

Application of tracer ratio and inverse dispersion methods with boat-based plume measurements to estimate ammonia emissions from seabird colonies

Ammonia emissions from two contrasting seabird colonies in Scotland were measured, based on the determination of atmospheric concentrations downwind of the colonies. Atmospheric concentrations of ammonia (NH₃) across the downwind plume were compared with the inverse application of a Gaussian dispersion model (ID) to calculate the modelled NH₃ emission that would generate the measured cross-wind-integrated plume concentration. In parallel, a tracer gas (sulphur hexafluoride, SF₆) was released from the colonies with air samples taken to allow determination of SF₆ concentrations. On the basis of the known emission rate of SF₆, the magnitude of ammonia emissions was estimated by the cross-wind-integrated tracer ratio (TR) of NH₃/SF₆ concentrations. Coupled with data on annual bird attendance, the measurements indicate annual emissions from the Isle of May and the Bass Rock of 18 and 132 tonnes NH₃-N year^?1, respectively. The measured NH₃ emissions were compared with estimates of seabird nitrogen excretion to estimate the proportion of excreted N that is volatilised as NH₃ (F _Nr). The emission estimates of the two methods compared favourably, giving 4 and 6 kg NH₃-N h^?1 (F _Nr = 15%) for the Isle of May for the ID and TR methods, respectively, and 21 and 25 kg NH₃-N h^?1 (F _Nr = 50%) for the Bass Rock for the ID and TR methods, respectively. The results provide the first measurement-based estimates to allow regional up scaling of ammonia emissions from seabirds.     

Analysis of the St. Petersburg Traffic Data using the OSPM Model

Since October 1998 two DOAS instruments were installed at the level of the first floor and at the top of a building located in St. Petersburg at Pestelya Street. The collected datacovers the time period of December 1998–March 2001, and include concentrations of benzene, toluene, NO and NO₂, ozone and SO₂. There is also an additional information about the traffic intensity and meteorological conditions. The results of the analysis of this data set, using the OSPM model, are presented here with the goal to understand the features of the air pollution dispersion in this street canyon and to analyse the information about the emission factors of the vehicles. In particular, the model results are used for the solution of the inverse problem of reconstructing the emission factors from measured concentrations. The results obtained indicate that most of the concentrations are well inside the Russian standards with the only exception of NO₂ (mean and 98-th percentile are equal to 57.8 and 119.2 g m^-3 for the street level). The same values for benzene are 18.5 and 62.6, respectively. Emission estimates show that there is a possibility that the NO_x and benzene basic emission factors recommended by the Russian national guidelines could result in overestimating the traffic emissions. These considerations are supplemented with the model sensitivity tests carried out in connection with the problem of predictability of NO₂ concentrations in the street canyon. Tests indicate that NO₂ concentrations are not very sensitive to NO_x emissions because of the usually low urban background ozone levels.     

Methane flux and oxidation at two types of intermediate landfill covers

Methane emissions were measured on two areas at a Florida (USA) landfill using the static chamber technique. Because existing literature contains few measurements of methane emissions and oxidation in intermediate cover areas, this study focused on field measurement of emissions at 15-cm-thick non-vegetated intermediate cover overlying 1-year-old waste and a 45-cm-thick vegetated intermediate cover overlying 7-year-old waste. The 45 cm thick cover can also simulate non-engineered covers associated with older closed landfills. Oxidation of the emitted methane was evaluated using stable isotope techniques. The arithmetic means of the measured fluxes were 54 and 22 g CH(4) m(-2)d(-1) from the thin cover and the thick cover, respectively. The peak flux was 596 g m(-2)d(-1) for the thin cover and 330 g m(-2)d(-1) for the thick cover. The mean percent oxidation was significantly greater (25%) at the thick cover relative to the thin cover (14%). This difference only partly accounted for the difference in emissions from the two sites. Inverse distance weighing was used to describe the spatial variation of flux emissions from each cover type. The geospatial mean flux was 21.6 g m(-2)d(-1) for the thick intermediate cover and 50.0 g m(-2)d(-1) for the thin intermediate cover. High emission zones in the thick cover were fewer and more isolated, while high emission zones in the thin cover were continuous and covered a larger area. These differences in the emission patterns suggest that different CH(4) mitigation techniques should be applied to the two areas. For the thick intermediate cover, we suggest that effective mitigation of methane emissions could be achieved by placement of individualized compost cells over high emission zones. Emissions from the thin intermediate cover, on the other hand, can be mitigated by placing a compost layer over the entire area.     

Application of tracer ratio and inverse dispersion methods with boat-based plume measurements to estimate ammonia emissions from seabird colonies

Ammonia emissions from two contrasting seabird colonies in Scotland were measured, based on the determination of atmospheric concentrations downwind of the colonies. Atmospheric concentrations of ammonia (NH₃) across the downwind plume were compared with the inverse application of a Gaussian dispersion model (ID) to calculate the modelled NH₃ emission that would generate the measured cross-wind-integrated plume concentration. In parallel, a tracer gas (sulphur hexafluoride, SF₆) was released from the colonies with air samples taken to allow determination of SF₆ concentrations. On the basis of the known emission rate of SF₆, the magnitude of ammonia emissions was estimated by the cross-wind-integrated tracer ratio (TR) of NH₃/SF₆ concentrations. Coupled with data on annual bird attendance, the measurements indicate annual emissions from the Isle of May and the Bass Rock of 18 and 132 tonnes NH₃-N year^–1, respectively. The measured NH₃ emissions were compared with estimates of seabird nitrogen excretion to estimate the proportion of excreted N that is volatilised as NH₃ (F_Nr). The emission estimates of the two methods compared favourably, giving 4 and 6 kg NH₃-N h^–1 (F_Nr = 15%) for the Isle of May for the ID and TR methods, respectively, and 21 and 25 kg NH₃-N h^–1 (F_Nr = 50%) for the Bass Rock for the ID and TR methods, respectively. The results provide the first measurement-based estimates to allow regional up scaling of ammonia emissions from seabirds.     

Epilithic Diatoms in an Alpine Lake (Traunsee,Austria) Affected by Soda and Salt Mining Industries

Traunsee, a 191 m deep Alpine lake in Austria, is affected by industrial tailings from the soda and salt mining industries since 1883. In 1998 littoral water chloride concentrations ranged between 40 and 85 mg L^-1 and the highest conductivity was 560 S cm^-1, which is almost double as high as the values reported from the two nearby reference lakes. Chloride concentrations increased towards the location of the industrial salt and soda emission into the lake. Analogously to the chloride gradient, the epilithic littoral diatom flora changes towards the waste inlet. Shifts in the species percentages towards the emission source, a high percentage of taxa with large conductivity tolerances, the presence of a small Achnanthes minutissima Kützing morphotype, and occurrences of taxa focused at habitats of higher electrolyte content, indicate subtle impacts on the epilithic diatom flora. An analysis of the seasonal succession of the epilithic diatoms at the waste inlet compared to a lake intern reference site, reveals that only during the late summer period in 1998 the diatom assemblage at the waste inlet became significantly different, indicating seasonally restricted effects of the industrial emissions.     

The spatial distribution of ammonia emitted from seabirds and its contribution to atmospheric nitrogen deposition in the UK

Simple bioenergetics models were used to derive annual nitrogen excretion rates of each seabird species occurring at colonies in the UK. These were combined with population distribution data and an estimated fraction of nitrogen volatilized to estimate the spatial distribution of NH₃ emissions from seabird colonies at a 1 km resolution. The effect of these emissions on atmospheric NH₃ concentrations and nitrogen deposition in the UK was assessed using the FRAME atmospheric chemistry and transport model. The total emission of NH₃ from the UK seabird colonies is estimated at 2.7 kt yr^–1. Emissions from seabirds are largely concentrated in remote parts of Britain, where agricultural and other anthropogenic emissions are minimal. Although seabirds account for less than 1% of total UK NH₃ emissions (370 kt yr^–1), their occurrence in remote areas and frequently large colony sizes results in seabirds providing a major fraction of the atmospheric nitrogen deposition for many remote ecosystems.     

Quantifying methane emission from fugitive sources by combining tracer release and downwind measurements – A sensitivity analysis based on multiple field surveys

Using a dual species methane/acetylene instrument based on cavity ring down spectroscopy (CRDS), the dynamic plume tracer dispersion method for quantifying the emission rate of methane was successfully tested in four measurement campaigns: (1) controlled methane and trace gas release with different trace gas configurations, (2) landfill with unknown emission source locations, (3) landfill with closely located emission sources, and (4) comparing with an Fourier transform infrared spectroscopy (FTIR) instrument using multiple trace gasses for source separation. The new real-time, high precision instrument can measure methane plumes more than 1.2 km away from small sources (about 5 kg h^?1) in urban areas with a measurement frequency allowing plume crossing at normal driving speed. The method can be used for quantification of total methane emissions from diffuse area sources down to 1 kg per hour and can be used to quantify individual sources with the right choice of wind direction and road distance. The placement of the trace gas is important for obtaining correct quantification and uncertainty of up to 36% can be incurred when the trace gas is not co-located with the methane source. Measurements made at greater distances are less sensitive to errors in trace gas placement and model calculations showed an uncertainty of less than 5% in both urban and open-country for placing the trace gas 100 m from the source, when measurements were done more than 3 km away. Using the ratio of the integrated plume concentrations of tracer gas and methane gives the most reliable results for measurements at various distances to the source, compared to the ratio of the highest concentration in the plume, the direct concentration ratio and using a Gaussian plume model. Under suitable weather and road conditions, the CRDS system can quantify the emission from different sources located close to each other using only one kind of trace gas due to the high time resolution, while the FTIR system can measure multiple trace gasses but with a lower time resolution.     

Effect of temperature on bacterial emissions in composting of swine manure

Swine manure was subjected to laboratory scale composting in order to quantify bioaerosols, i.e., airborne culturable bacteria and endotoxin, in the exhaust gas, which provided details on the effect of temperature on bacterial emissions. The concentration of airborne bacteria reached 31,250 colony-forming units (CFU)/m³ during the thermophilic stage of composting, and positively correlated with the temperature profile of the compost pile. Initially, the endotoxin concentration was 1820 endotoxin units (EU)/m³, but it decreased exponentially as the composting process proceeded. The temperature can be an excellent indicator of bacterial emissions during the composting process, indicating that the composting process requires a consistently high temperature to ensure sanitization of both compost and bacterial emissions. The cumulative emission data showed that emission factors was 11.2?13.5 CFU/g dry swine manure and that of endotoxin was 0.5?0.9 EU/g dry swine manure. The bacterial diversity in the bioaerosol was analyzed by polymerase chain reaction-denaturing gradient gel electrophoresis, revealing the presence of various gram-negative bacterial consortia.     

Long Term NH3 Flux Measurements above Grasslands in The Netherlands

Ammonia concentration gradients were measuredabove a grassland in an agricultural region fromJuly 1998 to July 2000 at the locationSchagerbrug in the Netherlands. They were used tocalculate the surface-atmosphere exchange ofammonia by means of the aerodynamic gradienttechnique. Measurements of the ammonia exchangewere also performed at a grass field that is partof a major wetland reserve in the centre of theNetherlands (Oostvaardersplassen), during theperiod June 1994–September 1995. At Schagerbrug,low net emissions or small depositions weremeasured during the winter months, and a netemission up to 5 kg NH₃ ha^-1 month^-1 in summer. The net annual emission was 26 kgN ha^-1, with manure application contributingabout 50% of this emission. AtOostvaardersplassen mainly deposition occurred,but large emissions were measured in autumn. Themeasured exchange fluxes are compared to modelevaluations that incorporate plant physiologicaldata, such as apoplastic NH₄ ⁺concentrations and pH. Results show a goodagreement between field observations and modelsimulations, although some improvements arenecessary during nighttime periods. Themeasurements are conducted within the GRAMINAEproject, a second tranche project of EC TERI.     

Influence of aeration on CH4, N2O and NH3 emissions during aerobic composting of a chicken manure and high C/N waste mixture

Co-composting of chicken manure, straw and dry grasses was investigated in a forced aeration system to estimate the effect of aeration rates on NH₃, CH₄ and N₂O emissions and compost quality. Continuous measurements of gas emissions were carried out and detailed gas emission patterns were obtained using an intermittent-aeration of 30 min on/30 min off at rates of 0.01 (A1), 0.1 (A2) and 0.2 (A3) m³ min⁻¹ m⁻³. Concentrations of CH₄ and N₂O at the low aeration rate (A1) were significantly greater than those at the other two rates, but there was no significant difference between the A2 and A3 treatments. CH₄ and N₂O emissions for this mixture could be controlled when the composting process was aerobic and ammonia emissions were reduced at a lower aeration rate. Comparison of CH₄, N₂O, NH₃ emissions and compost quality showed that the aeration rate of the A2 treatment was superior to the other two aeration rates.     

Laboratory evaluation of the pollution potential of land applied dairy manure

Laboratory experiments were performed using 24,900 mm deep soil columns to determine the amounts of nitrogen lost through the processes of leaching and ammonia volatilization from land receiving high applications of dairy cattle manure. The soil columns were conditioned over a period of one year before the start of the experiment and a conscious effort was made to make the physical properties of the columns soil sufficiently reproduced to resemble the undisturbed soil. The effects of three manure and three water application rates on nitrogen losses were monitored over a period of 10 weeks. The concentrations of nitrogen compounds in the leachates obtained from the soil columns were very low. The observed losses of nitrogen caused by leaching and ammonia volatilization were influenced by manure and water application rates. The high concentration of nitrate nitrogen at the beginning of the experiment has the potential of causing groundwater pollution. Also, ammonia volatilization is considered high enough to cause serious odor problems.     

Acidification at Plastic Lake,Ontario: Has 20 Years Made a Difference?

In response to reduced sulphur emissions, there has been a large decrease in sulphate (; −0.97 μeq l⁻¹ year⁻¹) and hydrogen (−1.18 μeq l⁻¹ year⁻¹) ion concentration in bulk precipitation between 1980 and 2000 at Plastic Lake in central Ontario. The benefit of this large reduction in deposition on stream water chemistry was assessed using the gauged outflow from a conifer-forested catchment (PC1; 23.3 ha), which is influenced by a small wetland located immediately upstream of the outflow. Sulphate concentrations declined, but not significantly due to large inter-annual variation in concentration. Between 1980 and 2000, there were significant increases in dissolved organic carbon, ammonium and potassium concentration likely reflecting increased mineralisation in the wetland. Calcium concentrations in PC1 decreased during the two decade period (−2.24 μeq l⁻¹ year⁻¹), as a consequence there was no improvement in stream pH and the Ca:Al ratio in PC1 continued to decline. A similar response was noted in an upland-draining sub-catchment of PC1-08 that has been monitored since 1987. Despite large reductions in deposition and almost complete retention of nitrogen in soil, there has been no improvement (in terms of pH) in stream water at PC1 due to a combination of soil acidification and climatic (droughts, increased mineralisation) perturbations.     

Future landfill emissions and the effect of final cover installation--a case study

Municipal solid waste (MSW) landfills are potential long-term sources of emissions. Hence, they need to be managed after closure until they do not pose a threat to humans or the environment. The case study on the Breitenau MSW landfill was performed to evaluate future emission levels for this site and to illustrate the effect of final cover installation with respect to long-term environmental risks. The methodology was based on a comprehensive assessment of the state of the landfill and included analysis of monitoring data, investigations of landfilled waste, and an evaluation of containment systems. A model to estimate future emission levels was established and site-specific predictions of leachate emissions were presented based on scenario analysis. The results are used to evaluate the future pollution potential of the landfill and to compare different aftercare concepts in view of long-term emissions. As some leachable substances became available for water flow during cover construction due to a change in the water flow pattern of the waste, a substantial increase in leachate concentrations could be observed at the site (e.g. concentrations of chloride increased from 200 to 800 mg/l and of ammonia-nitrogen from 140 to about 500 mg/l). A period of intensive flushing before the final cover installation could have reduced the amount of leachable substances within the landfill body and rapidly decreased the leachate concentrations to 11 mg Cl/l and 79 mg NH₄-N/l within 50 years. Contrarily, the minimization of water infiltration is associated with leachate concentrations in a high range for centuries (above 400 mg Cl/l and 200 mg NH₄-N/l) with low concomitant annual emission loads (below 12 kg/year of Cl or 9 kg/year of NH₄-N, respectively). However, an expected gradual decrease of barrier efficiency over time would be associated with higher emission loads of 50 kg of chloride and 30 kg of ammonia-nitrogen at the maximum, but a faster decrease of leachate concentration levels.     

The effect of dust emissions from open storage piles to particle ambient concentration and human exposure

The current study focus on the determination of dust emissions from piles in open storage yards of a municipal solid waste (MSW) composting site and the subsequent atmospheric dust dispersion. The ISC3-ST (Industrial Source Complex Version 3 – Short Term) model was used for the evaluation of the PM₁₀ ambient concentrations associated with the dispersion of MSW compost dust emissions in air. Dust emission rates were calculated using the United States Environmental Protection Agency proposed dust resuspension formulation from open storage piles using local meteorological data. The dispersion modelling results on the spatial distribution of PM₁₀ source depletion showed that the maximum concentrations were observed at a distance 25–75 m downwind of the piles in the prevailing wind direction. Sensitivity calculations were performed also to reveal the effect of the compost pile height, the friction velocity and the receptor height on the ambient PM₁₀ concentration. It was observed that PM₁₀ concentrations (downwind in the prevailing wind direction) increased with increasing the friction velocity, increasing the pile height (for distances greater than 125 m from the source) and decreasing the receptor height (for distances greater than 125 m from the source). Furthermore, the results of ISC3-ST were analysed with the ExDoM (Exposure Dose Model) human exposure model. The ExDoM is a model for calculating the human exposure and the deposition dose, clearance, and finally retention of aerosol particles in the human respiratory tract (RT). PM₁₀ concentration at the composting site was calculated as the sum of the concentration from compost pile dust resuspension and the background concentration. It was found that the exposure to PM₁₀ and deposited lung dose for an adult Caucasian male who is not working at the composting site is less by 20–74% and 29–84%, respectively, compared to those for a worker exposed to PM concentrations at the composting site.     

Hydrogen sulfide flux measurements from construction and demolition debris (C&D) landfills

Hydrogen sulfide (H2S) has been identified as a principal odorous component of gaseous emissions from construction and demolition debris (C&D) landfills. Although several studies have reported the ambient concentrations of H2S near C&D landfills, few studies have quantified emission rates of H2S. One of the most widely used techniques for measuring surface gas emission rates from landfills is the flux chamber method. Flux measurements using the flux chamber were performed at five different C&D landfills from April to August, 2003. The flux rates of H2S measured in this research were between 0.192 and 1.76 mg/(m2-d).     

Emissions from baled municipal solid waste: II. Effects of different treatments and baling techniques on the emission of volatile organic compounds.

This paper focuses on the volatile organic compound emissions from baled municipal solid waste (MSW). The analytical methodology was based on sampling with adsorbent tubes once a month during seven occasions within a time period of 1 year. Automated analyses were carried out on-line work-up with thermal desorption directly connected to a gas chromatograph-mass spectrometer. The effect of different baling techniques, cylindrical and rectangular baling was compared. It was found that cylindrically baled MSW emitted larger concentration of esters than their rectangular counter parts. Conversely, aromatic compounds emissions dominated in rectangularly baled MSW. This indicates that different degradation mechanisms operate in the waste bales. Cylindrical and rectangular bales are generally wrapped with six layers of 250 microm thick low density polyethylene (LDPE). It was observed that by wrapping an extra six layers of LDPE film onto the bales, the emissions from cylindrical bales increased while emissions from the rectangular counterpart decreased. Over time, the volatile organic compound emissions from cylindrical bales decreased two orders of magnitudes from 96.2 +/- 20.8 microg m(-3) in September 2003 to 0.80 +/- 0.07 microg m(-3) in July 2004. The rectangular bales exhibited an almost identical relative emission reduction from 54.4 +/- 4.3 microg m(-3) in September 2003 to 0.46 +/- 0.02 microg m(-3) in July 2004. Future work will concentrate on full-scale storages, taking into account waste type, storage size, temperature development and the different baling techniques among other variables.     

Long Term Trends in Sulphur and Nitrogen Deposition in Europe and the Cause of Non-linearities

Emissions of sulphur and oxidized nitrogen compounds in Europe have been reduced following a series of control measures during the last two decades. These changes have taken place during a period in which the primary gases and the wet deposition throughout Europe were extensively monitored. Since the end of the 1970s, for example land based sulphur emissions declined by between 90 and 70% depending on the region. Over the same period the total deposition of sulphur and its partitioning into wet and dry deposition have declined, but the spatial pattern in the reduction in deposition differs from that of emission and has changed with time. Such non-linearities in the emission-deposition relationship are important to understand as they complicate the process of assessing the effects of emission reduction strategies. Observed non-linearities in terrestrial sulphur emission-deposition patterns have been identified in north west Europe due to increases in marine emissions, and are currently slowing the recovery of freshwater ecosystems. Changes in the relative amounts of SO₂ and NH₃ in air over the last two decades have also changed the affinity of terrestrial surfaces for SO₂ and have therefore changed the deposition velocity of SO₂ over substantial areas. The consequence of this effect has been the very rapid reduction in ambient SO₂ concentration in some of the major source areas of Europe, where NH₃ did not change much. Interactions between the different pollutants, generating non-linearities are now being incorporated in long-range transport models to simulate the effects of historical emission trends and to provide projections into the future. This paper identifies non-linearities in emission deposition relationships for sulphur and nitrogen compounds in Europe using data from the EMEP long-rang transport model and measured concentration fields of the major ions in precipitation and of SO₂ and NO₂ in surface air.