Comparison of measured and model-calculated real-world traffic emissions

The quality of an emission calculation model based on emission factors measured on roller test stands and statistical traffic data was evaluated using source strengths and emission factors calculated from real-world exhaust gas concentration differences measured upwind and downwind of a motorway in southwest Germany. Gaseous and particulate emissions were taken into account. Detailed traffic census data were taken during the measurements. The results were compared with findings of similar studies.The main conclusion is the underestimation of CO and NO_x source strengths by the model. On the average, it amounts to 23% in case of CO and 17% for NO_x. The latter underestimation results from an undervaluation by 22% of NO_x emission factors of heavy-duty vehicles (HDVs). There are significant differences between source strengths on working days and weekends because of the different traffic split between light-duty vehicles (LDVs) and HDVs. The mean emission factors of all vehicles from measurements are 1.08 g km⁻¹ veh⁻¹ for NO_x and 2.62 g km⁻¹ veh⁻¹ for CO. The model calculations give 0.92 g km⁻¹ veh⁻¹ for NO_x and 2.14 g km⁻¹ veh⁻¹ for CO.The source strengths of 21 non-methane hydrocarbon (NMHC) compounds quantified are underestimated by the model. The ratio between the measured and model-calculated emissions ranges from 1.3 to 2.1 for BTX and up to 21 for 16 other NMHCs. The reason for the differences is the insufficient knowledge of NMHC emissions of road traffic.Particulate matter emissions are dominated by ultra-fine particles in the 10–40 nm range. As far as aerosols larger than 29 nm are concerned, 1.80×10¹⁴ particles km⁻¹ veh⁻¹ are determined for all vehicles, 1.22×10¹⁴ particles km⁻¹ veh⁻¹ and an aerosol volume of 0.03 cm³ km⁻¹ veh⁻¹ are measured for LDVs, and for HDVs 7.79×10¹⁴ particles km⁻¹ veh⁻¹ and 0.41 cm³ km⁻¹ veh⁻¹ are calculated. Traffic-induced turbulence has been identified to have a decisive influence on exhaust gas dispersion near the source.     

Atmospheric deposition of nitrogen emitted in the Metropolitan Area of Buenos Aires to coastal waters of de la Plata River

The Metropolitan Area of Buenos Aires (MABA) is the third mega-city in Latin America. Atmospheric N emitted in the area deposits to coastal waters of de la Plata River. This study describes the parameterizations included in DAUMOD-RD (v.3) model to evaluate concentrations of nitrogen compounds (nitrogen dioxide, gaseous nitric acid and nitrate aerosol) and their total (dry and wet) deposition to a water surface. This model is applied to area sources and CALPUFF model to point sources of NO_x in the MABA. The models are run for 3 years of hourly meteorological data, with a spatial resolution of 1 km². Mean annual deposition is 69, 728 kg-N year^?1 over 2 339 km² of river. Dry deposition contributions of N-NO₂, N-HNO₃ and N-NO₃^? to this value are 44%, 22% and 20%, respectively. Wet deposition of N-HNO₃ and N-NO₃^? represents 3% and 11% of total annual value, respectively. This very low contribution results from the rare occurrence of rainy hours with wind blowing from the city to the river. Monthly dry deposition flux estimated for coastal waters of MABA varies between 7 and 13 kg-N km^?2 month^?1. These results are comparable to values reported for other coastal zones in the world.     

Spatial distribution of wet deposition of nitrogen in South Korea

A method is developed to estimate wet deposition of nitrogen in a 11×14 km (0.125°Lon.×0.125°Lat.) grid scale using the precipitation chemistry monitored data at 10 sites scattered over South Korea supplemented by the routinely available precipitation rate data at 65 sites and the estimated emissions of NO₂ and NH₃ at each precipitation monitoring site. This approach takes into account the contributions of local NO₂ and NH₃ emissions and precipitation rates on wet deposition of nitrogen. Wet deposition of nitrogen estimated by optimum regression equations for NO₃⁻ and NH₄⁺ derived from annual total monitored wet deposition and that of emissions of NO₂ and NH₃ is incorporated to normalize wet deposition of nitrogen at each precipitation rate class, which is divided into 6 classes. The optimum regression equations for the estimation of wet deposition of nitrogen at precipitation monitoring sites are developed using the normalized wet deposition of nitrogen and the precipitation rate at 10 precipitation chemistry monitoring sites. The estimated average annual total wet depositions of NO₃⁻ and NH₄⁺ are found to be 260 and 500 eq ha⁻¹ yr⁻¹ with the maximum values of 400 and 930 eq ha⁻¹ yr⁻¹, respectively. The annual mean total wet deposition of nitrogen is found to be about 760 eq ha⁻¹ yr⁻¹, of which more than 65% is contributed by wet deposition of ammonium while, the emission of NH₃ is about half of that of NO₂, suggesting the importance of NH₃ emission for wet deposition of nitrogen in South Korea.     

Measurement and analysis of atmospheric ammonia emissions from anaerobic lagoons

Ammonia-nitrogen flux (NH₃-N=(14/17)NH₃) was determined from six anaerobic swine waste storage and treatment lagoons (primary, secondary, and tertiary) using the dynamic chamber system. Measurements occurred during the fall of 1998 through the early spring of 1999, and each lagoon was examined for approximately one week. Analysis of flux variation was made with respect to lagoon surface water temperature (∼15 cm below the surface), lagoon water pH, total aqueous phase NH_x(=NH₃+NH₄⁺) concentration, and total Kjeldahl nitrogen (TKN). Average lagoon temperatures (across all six lagoons) ranged from approximately 10.3 to 23.3^°C. The pH ranged in value from 6.8 to 8.1. Aqueous NH_x concentration ranged from 37 to 909 mg N l⁻¹, and TKN varied from 87 to 950 mg N l⁻¹. Fluxes were the largest at the primary lagoon in Kenansville, NC (March 1999) with an average value of 120.3 μg N m⁻² min⁻¹, and smallest at the tertiary lagoon in Rocky Mount, NC (November 1998) at 40.7 μg N m⁻² min⁻¹. Emission rates were found to be correlated with both surface lagoon water temperature and aqueous NH_x concentration. The NH₃-N flux may be modeled as ln(NH₃-N flux)=1.0788+0.0406T_L+0.0015([NH_x]) (R²=0.74), where NH₃-N flux is the ammonia flux from the lagoon surface in μg N m⁻² min⁻¹, T_L is the lagoon surface water temperature in ^°C, and [NH_x] is the total ammonia-nitrogen concentration in mg N l⁻¹.     

Estimation of wind blown dust emissions in Europe and its vicinity

The assessment of the wind blown dust emission for Europe and selected regions of North Africa and Southwest Asia was carried out using a mesoscale model. The mesoscale model was parameterized based on the current literature review. The model provides data on PM₁₀ emission from several dust reservoirs (anthropogenic, agriculture, semi- and natural) with spatial resolution of 10 × 10 km and temporal resolution of 1 h. The spatial variability of PM₁₀ emission depends on soil texture, land cover/land use as well as meteorological conditions. Lands covered with water or permanently wet were excluded from the model. The land covered with vegetation is treated as dust reservoir whose dust emission capacity depends on the type of vegetation and cover. The dust reservoirs are divided into reservoirs with stable and unstable surface. The changes of emission in time depend on meteorological parameters.The wind blown dust emission should be treated as a non-continuous spatio-temporal process. The emissions are estimated with high uncertainty. The estimated PM₁₀ yearly total load emitted by wind from the European territory is highly differentiated in space and time and is equal to 0.74 Tg. The total load of PM₁₀ emitted by wind from North African and Southwest Asian land surface located in the vicinity of European boundaries is assessed as nearly 50% (0.43 Tg) of the total load estimated for the whole Europe.The average yearly PM₁₀ emission factor for Europe was estimated at 0.139 Mg km^?2.The PM₁₀ emission from agricultural areas is estimated at 52% of the total wind blown emission from the domain of the European Union project “Improving and applying methods for the calculation of natural and biogenic emissions and assessment of impacts to the air quality” - NatAir.PM₁₀ emission factor for natural areas of Europe is estimated at 0.021 Mg km^?2. Appropriate factors for agricultural areas and anthropogenic areas are 0.157 Mg km^?2 and 0.118 Mg km^?2, respectively. The latter two factors are probably underestimated due to omitting in the model of other dust emission mechanisms than aeolian erosion.     

Continuous gaseous and total ammonia measurements from the southeastern aerosol research and characterization (SEARCH) study

Continuous ammonia (NH₃) measurements with a temporal resolution of 5 min were implemented at selected SEARCH sites in the southeastern U. S. during 2007. The SEARCH continuous NH₃ instrument uses a citric acid denuder difference technique employing a dual-channel nitric oxide-ozone chemiluminescence analyzer. Data from two SEARCH sites are presented, Jefferson Street, Atlanta (JST) (urban), and Yorkville, Georgia (YRK) (rural), for the period July–December, 2007. Highest NH_x (total ammonia = gaseous NH₃ + PM_2.5 NH₄⁺) values were observed in August and September at both JST and YRK. Highest NH₃ values occurred in August and September at JST, but in August through October at YRK. Lowest NH₃ and NH_x values occurred in December at both sites. YRK is significantly impacted by nearby poultry sources, routinely experiencing hourly average NH₃ mixing ratios above 20 ppbv. Wind sector analysis clearly implicates the nearby poultry operations as the source of the high NH₃ values. Weekday versus weekend differences in composite hourly mean diurnal profiles of NH₃ at JST indicate that mobile sources have a measurable but relatively small impact on NH₃ observed at that site, and little or no impact on NH₃ observed at YRK. A distinctive composite mean hourly diurnal variation was observed at both JST and YRK, exhibiting maxima in the morning and evening with a broad minimum during midday. Analysis of observed NH₃ diurnal variations from the literature suggests a hypothesized mechanism for the observed behavior based on interaction of local emissions and dry deposition with the formation and collapse of the dynamically mixed atmospheric boundary layer during the day and shallow nocturnal layer at night. Simple mixed layer concentration box model simulations confirm the plausibility of the suggested mechanism.     

Concentration-dependent NH3 deposition processes for moorland plant species with and without stomata

Currently, in operational modelling of NH₃ deposition a fixed value of canopy resistance (R_c) is generally applied, irrespective of the plant species and NH₃ concentration. This study determined the effect of NH₃ concentration on deposition processes to individual moorland species. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to Deschampsia cespitosa (L.) Beauv., Calluna vulgaris (L.) Hull, Eriophorum vaginatum L., Cladonia spp., Sphagnum spp., and Pleurozium schreberi (Brid.) Mitt. Measurements were conducted across a wide range of NH₃ concentrations (1–140 μg m⁻³).NH₃ concentration directly affects the deposition processes to the vegetation canopy, with R_c, and cuticular resistance (R_w) increasing with increasing NH₃ concentration, for all the species and vegetation communities tested. For example, the R_c for C. vulgaris increased from 14 s m⁻¹ at 2 μg m⁻³ to 112 s m⁻¹ at 80 μg m⁻³. Diurnal variations in NH₃ uptake were observed for higher plants, due to stomatal uptake; however, no diurnal variations were shown for non-stomatal plants. R_c for C. vulgaris at 80 μg m⁻³ was 66 and 112 s m⁻¹ during day and night, respectively. Differences were found in NH₃ deposition between plant species and vegetation communities: Sphagnum had the lowest R_c (3 s m⁻¹ at 2 μg m⁻³ to 23 at 80 μg m⁻³), and D. cespitosa had the highest nighttime value (18 s m⁻¹ at 2 μg m⁻³ to 197 s m⁻¹ at 80 μg m⁻³).     

Regional dispersion of oxidized sulfur in Central Chile

Chile has a long tradition of exploiting mineral resources, particularly copper (Cu). One of the largest Cu smelters, Caletones, located some 150 km south of the country's capital, Santiago, in Central Chile, is responsible for about 0.4% of about 70 Tg S/yr oxidized sulfur (SO_x) emitted by anthropogenic sources worldwide. Santiago, a megacity with 5 million inhabitants, stands for about 5 Gg S/yr. The average meteorological conditions are unfavorable for the dispersion of pollutants in this area. All this poses risks for human health and vegetation. Also, downwind from these polluted areas there may be large-scale impacts on cloud properties and on oxidative cycles. Here, we present the first attempt to assess the regional distribution of SO_x in Central Chile using a dispersion model (MATCH) driven with data from a limited area weather forecast model (HIRLAM). Emphasis has been given to the impact of Cu smelters upon urban air quality, particularly that of Santiago. Six 1-month long periods were simulated for the years 1997, 1998 and 1999. These periods span over a broad range of typical meteorological conditions in the area including El Niño and La Niña years. Estimates of the regional dispersion and deposition patterns were calculated. The emissions from the large Cu smelters dominate the distribution of SO_x. A budget of SO_x over an area of 200×200 km² around Santiago is presented. There is too low a number of monitoring stations to perform a detailed evaluation of MATCH. Nevertheless, the model reproduces consistently all the regional-scale characteristics that can be derived from the available observations.     

Decadal reductions of traffic emissions on a transit route in Austria – results of the Tauerntunnel experiment 1997

Real-world emissions of a traffic fleet on a transit route in Austria were determined in the Tauerntunnel experiment in October 1997. The total number of vehicles and the average speed was nearly the same on both measuring days (465 vehicles 30 min⁻¹ and 76 km h⁻¹ on the workday, 477 and 78 km h⁻¹ on Sunday). The average workday fleet contained 17.6% heavy-duty vehicles (HDV) and the average Sunday fleet 2.8% HDV resulting in up to four times higher emission rates per vehicle per km on the workday than on Sunday for most of the regulated components (CO₂, CO, NO_x, SO₂, and particulate matter-PM10). Emission rates of NMVOC accounted for 200 mg vehicle⁻¹ km⁻¹ on both days. The relative contributions of light-duty vehicles (LDV) and HDV to the total emissions indicated that aldehydes, BTEX (benzene, toluene, ethylbenzene, xylenes), and alkanes are mainly produced by LDV, while HDV dominated emissions of CO, NO_x, SO₂, and PM10. Emissions of NO_x caused by HDV were 16,100 mg vehicle⁻¹ km⁻¹ (as NO₂). Produced by LDV they were much lower at 360 mg vehicle⁻¹ km⁻¹. Comparing the emission rates to the results that were obtained by the 1988 experiment at the same place significant changes in the emission levels of hydrocarbons and CO, which accounted 1997 to only 10% of the levels in 1988, were noticed. However, the decrease of PM has been modest leading to values of 80 and 60% of the levels in 1988 on the workday and on Sunday, respectively. Emission rates of NO_x determined on the workday in 1997 were 3130 mg vehicle⁻¹ km⁻¹ and even higher than in 1988 (2630 mg vehicle⁻¹ km⁻¹), presumable due to the increase of the HD-traffic.     

Concentration-dependent NH3 deposition processes for mixed moorland semi-natural vegetation

Dry deposition modelling typically assumes that canopy resistance (R_c) is independent of ammonia (NH₃) concentration. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to a moorland composed of a mixture of Calluna vulgaris (L.) Hull, Eriophorum vaginatum L. and Sphagnum spp. Ammonia was applied at a wide range of concentrations (1–100 μg m⁻³). The physical and environmental properties and the testing of the chamber are described, as well as results for the moorland vegetation using the ‘canopy resistance’ and ‘canopy compensation point’ interpretations of the data.Results for moorland plant species demonstrate that NH₃ concentration directly affects the rate of NH₃ deposition to the vegetation canopy, with R_c and cuticular resistance (R_w) increasing with increasing NH₃ concentrations. Differences in R_c were found between night and day: during the night R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 95 s m⁻¹ at 80 μg m⁻³, whereas during the day R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 48 s m⁻¹ at 80 μg m⁻³. The lower resistance during the day is caused by the stomata being open and available as a deposition route to the plant. R_w increased with increasing NH₃ concentrations and was not significantly different between day and night (at 80 μg m⁻³ NH₃ day R_w=88 s m⁻¹ and night R_w=95 s m⁻¹). The results demonstrate that assessments using fixed R_c will over-estimate NH₃ deposition at high concentrations (over ∼15 μg m⁻³).     

Validation of model calculation of ammonia deposition in the neighbourhood of a poultry farm using measured NH3 concentrations and N deposition

Substantial emission of ammonia (NH₃) from animal houses and the related high local deposition of NH₃-N are a threat to semi-natural nitrogen-deficient ecosystems situated near the NH₃ source. In Denmark, there are regulations limiting the level of NH₃ emission from livestock houses near N-deficient ecosystems that are likely to change due to nitrogen (N) enrichment caused by NH₃ deposition. The models used for assessing NH₃ emission from livestock production, therefore, need to be precise, as the regulation will affect both the nature of the ecosystem and the economy of the farmer. Therefore a study was carried out with the objective of validating the Danish model used to monitor NH₃ transport, dispersion and deposition from and in the neighbourhood of a chicken farm. In the study we measured NH₃ emission with standard flux measuring methods, NH₃ concentrations at increasing distances from the chicken houses using passive diffusion samplers and deposition using ¹⁵N-enriched biomonitors and field plot studies. The dispersion and deposition of NH₃ were modelled using the Danish OML-DEP model. It was also shown that model calculations clearly reflect the measured NH₃ concentration and N deposition. Deposition of N measured by biomonitors clearly reflected the variation in NH₃ concentrations and showed that deposition was not significantly different from zero (P < 0.05) at distances greater than 150–200 m from these chicken houses. Calculations confirmed this, as calculated N deposition 320 m away from the chicken farm was only marginally affected by the NH₃ emission from the farm. There was agreement between calculated and measured deposition showing that the model gives true estimates of the deposition in the neighbourhood of a livestock house emitting NH₃.     

Ammonia fluxes and derived canopy compensation points over non-fertilized agricultural grassland in The Netherlands using the new gradient ammonia—high accuracy—monitor (GRAHAM)

During a measurement period from June till November 2004, ammonia fluxes above non-fertilized managed grassland in The Netherlands were measured with a Gradient Ammonia—High Accuracy—Monitor (GRAHAM). Compared with earlier ammonia measurement systems, the GRAHAM has higher accuracy and a quality control system.Flux measurements are presented for two different periods, i.e. a warm, dry summer period (from 18 July till 15 August) and a wet, cool autumn period (23 September till 23 October). From these measurements canopy compensation points were derived. The canopy compensation point is defined as the effective surface concentration of ammonia. In the summer period (negative) deposition fluxes are observed in the evening, night and early morning due to leaf surface wetness, while in the afternoon emission fluxes are observed due to high canopy compensation points. The mean NH₃-flux in this period was 4 ng m⁻² s⁻¹, which corresponds to a net emission of 0.10 kg N ha⁻¹ over the 28 day sampling period. The NH₃-flux in the autumn period mainly shows (negative) deposition fluxes due to small canopy compensation points caused by low temperatures and a generally wet surface. The mean NH₃-flux in this period is −24 ng m⁻² s⁻¹, which corresponds to a net deposition of 0.65 kg N ha⁻¹ over the 31 day sampling period.Frequency distributions of the NH₃-concentration and flux show that despite higher average ambient NH₃-concentrations (13.3 μg m⁻³ in the summer period vs. 6.4 μg m⁻³ in the autumn period) there are more emission events in the summer period than in the autumn period (about 50% of the time in summer vs. 20% in autumn). This is caused by the high canopy compensation points in summer due to high temperatures and a dry surface. In autumn, deposition dominates due to a generally wet surface that induces low canopy compensation points.For our non-fertilized agricultural grassland site, the derived canopy compensation points (at temperatures between 7 and 29 °C) varied from 0.5 to 29.7 μg m⁻³ and were on an average 7.0 μg m⁻³, which is quite high for non-fertilized conditions and probably caused by high nitrogen inputs in the past or high dry deposition amounts from local sources. The average value for the ratio between NH₄⁺ and H⁺ concentration in the canopy, Γ_c, that was derived from our data was 2200.     

The use of inferential models for estimating nitric acid vapor deposition to semi-arid coniferous forests

Urban areas emit significant amounts of pollutants that impact forest ecosystems. One of the most important of these is nitric acid vapor (HNO₃), a nitrogen-containing gas that deposits efficiently to forest canopies. Since measuring HNO₃ fluxes directly is often impractical and costly in remote forest locales, inferential techniques are most often used to estimate HNO₃ flux. Given the highly efficient deposition of HNO₃, many of these inferential models assume that leaf surfaces are a ‘perfect sink’ for HNO₃ (i.e., that resistance to HNO₃ deposition is negligibly small or zero). This study tests the ‘perfect sink’ assumption in an open gas exchange system by exposing Abies magnifica, Abies concolor, and Pinus jeffreyi seedlings to concentrations of 1–13 ppb at 4–20% relative humidity. We find that, at these humidities and concentrations, cuticles are not perfect sinks for HNO₃, with cuticular resistance values ranging from 20 to 184 s m⁻¹. In addition, our results indicate that accumulating HNO₃ on leaf cuticles at these concentrations leads to higher cuticular resistance over 8–12 h exposure periods. Based on this laboratory data, we then parameterized cuticular resistance using a single-layer inferential model for semi-arid forests in the Lake Tahoe Basin. Modeled fluxes using this modification were 33% lower during well-mixed daytime conditions than the fluxes from an identical model run using the perfect sink assumption. Since HNO₃ can often account for more than half of atmospheric deposition, we conclude that inferential models that assume foliage to be perfect HNO₃ sinks are inaccurate, especially in semi-arid forests where significant amounts of HNO₃ can accumulate on leaf surfaces during dry periods.     

Modelling atmospheric mercury transport and deposition across Europe and the UK

There are inadequate measurements of surface ambient concentrations of mercury species and their deposition rates for the UK deposition budget to be characterized. In order to estimate the overall mercury flux budget for the UK, a simple long-term 1D Lagrangian trajectory model was constructed that treats emissions (1998), atmospheric transformation and deposition across Europe. The model was used to simulate surface concentrations of mercury and deposition across Europe at a resolution of 50 km×50 km and across the UK at 20 km×20 km. The model appeared to perform adequately when compared with the few available measurements, reproducing mean concentrations of elemental gaseous mercury at particular locations and the magnitude of regional gradients. The model showed that 68% of the UK's mercury emissions are exported and 32% deposited within the UK. Of deposition to the UK, 25% originates from the Northern Hemisphere/global background, 41% from UK sources and 33% from other European countries. The total mercury deposition to the UK is in good agreement with other modelling, 9.9 tonne yr⁻¹ cf. 9.0 tonne yr⁻¹, for 1998. However, the attribution differs greatly from the results of other coarser-scale modelling, which allocates 55% of the deposition to the UK from UK sources, 4% from other European countries and 60% from the global background atmosphere. The model was found to be sensitive to the speciation of emissions and the dry deposition velocity of elemental gaseous mercury. The uncertainties and deficiencies are discussed in terms of model parameterization and input data, and measurement data with which models can be validated. There is an urgent requirement for measurements of removal terms, concentrations, and deposition with which models can be parameterized and validated.     

Long-term measurements of SO2 dry deposition over Gansu Province,China

Potassium carbonate sulfation plates, monitored monthly for 11 years from 48 sites in 11 cities in Gansu Province, China, provide a crude estimate of cumulative SO₂ dry depositions. Measured SO₂ dry deposition rates were 1.6–472 mg m⁻² day⁻¹ and had seasonal variations with maxima in winter and minima mainly during summer as a result of higher winter and lower summer SO₂ concentrations. The 11-year monthly average SO₂ dry deposition rates are 23.2–248.97 and 11.7–175.6 mg m⁻² day⁻¹ in the eleven cities in winter and summer, respectively. A monthly average SO₂ deposition velocity was also estimated from 0.06 to 9.72 cm s⁻² in the 11 cities studied with a 11-year average maximum value of about 1.1–2.7 cm s⁻² in April and July and a 11-year average minimum value of about 0.2–1.0 cm s⁻¹ in January. The SO₂ dry deposition velocity also exhibits an increasing with wind speed in basins of less than 500 mm annual precipitation. In contrast, due to influences of the relative humidity in valleys of more than 500 mm annual precipitation, it shows a decreasing trend with wind speed increasing.     

Dry deposition of ammonia,nitric acid,ammonium, and nitrate to alpine tundra at Niwot Ridge,Colorado

Micrometeorological measurements and ambient air samples, analyzed for concentrations of NH₃, HNO₃, NH₄⁺, and NO₃⁻, were collected at an alpine tundra site on Niwot Ridge, Colorado. The measured concentrations were extremely low and ranged between 5 and 70 ng N m⁻³. Dry deposition fluxes of these atmospheric species were calculated using the micrometeorological gradient method. The calculated mean flux for NH₃ indicates a net deposition to the surface and indicates that NH₃ contributed significantly to the total N deposition to the tundra during the August–September measurement period. Our pre-measurement estimate of the compensation point for NH₃ in air above the tundra was 100–200 ng N m⁻³; thus, a net emission of NH₃ was expected given the low ambient concentrations of NH₃ observed. Based on our results, however, the NH₃ compensation point at this alpine tundra site appears to have been at or below about 20 ng N m⁻³. Large deposition velocities (>2 cm s⁻¹) were determined for nitrate and ammonium and may result from reactions with surface-derived aerosols.     

Historical changes in atmospheric nitrogen deposition to Cape Cod,Massachusetts, USA

We reconstructed the historical trends in atmospheric deposition of nitrogen to Cape Cod, Massachusetts, from 1910 to 1995 by compiling data from literature sources, and adjusting the data for geographical and methodological differences. The reconstructed data suggest that NO₃-N wet deposition to this region increased from a low of 0.9 kg N ha⁻¹ yr⁻¹ in 1925 to a high of approximately 4 kg N ha⁻¹ yr⁻¹ around 1980. The trend in NO₃-N deposition has remained since the early 1980s at around 3.6 kg N ha⁻¹ yr⁻¹. In contrast, NH₄-N wet deposition decreased from more than 4 kg N ha⁻¹ yr⁻¹ in the mid 1920s to about 1.5 kg N ha⁻¹ yr⁻¹ from the late-1940s until today. Emissions of NO_x-N in the Cape Cod airshed increased at a rate of 2.1 kg N ha⁻¹ per decade since 1910, a rate that is an order of magnitude higher than NO₃-N deposition. Estimates of NH₃ emissions to the northeast United States and Canada have decreased slightly throughout the century, but the decrease in reconstructed N-NH₄⁺ deposition rates does not parallel emissions estimates. The trend in reconstructed total nitrogen deposition suggests an overall increase through the century at a rate of 0.26 kg N ha⁻¹ per decade. This overall increase in deposition may expose coastal forests to rates of nitrogen addition that, if exceeded, could induce nitrogen saturation and increase nitrogen loads to adjoining estuaries.     

Regional modelling of anthropogenic sulphur in Southeast Asia

A co-operative research project between the Malaysian Meteorological Service (MMS) and the Swedish Meteorological and Hydrological Institute (SMHI) focussing on the usage of an atmospheric transport and chemistry model, has just been initiated. Here, we describe the main features of the dispersion model and discuss a first set of calculations in light of available measurements of sulphuric species in Southeast Asia. According to our results, anthropogenic sulphur concentrations and depositions are particularly high near the large cities of the region, around a metal smelter in the southern Philippines, and in a region extending from northern Vietnam into southeastern China. These areas coincide with the high-emissions regions of Southeast Asia and we tentatively conclude that regional transport of acidifying species is not as far-reaching as in the mid-latitudes. From our calculations, and from supporting measurements we conclude that most of rural Southeast Asia is not yet severely affected by anthropogenic sulphur, but given the rapid rate of economical development in this region the situation may deteriorate quickly. Areas that are particularly at risk include the large cities, northern Vietnam, most of central Thailand, most of peninsular Malaysia, eastern Sumatra and parts of Java, all of which receive total-sulphur depositions in excess of 0.5 g S m⁻² yr⁻¹. Our model simulates sulphate in precipitation in accordance with measurements, but it has a tendency to overestimate atmospheric SO₂. It remains to be investigated whether this is a problem in the model formulation or a result of unrepresentative sampling. An immediate continuation of this study should be performed with higher spatial resolution than the currently used 100×100 km². Other imperfections in this model study, which should be addressed in future work, include parameterised vertical transport in deep convective clouds, the influence of natural emissions (primarily from volcanoes) on the concentration and deposition of sulphuric species, and the year-to-year variability of the driving meteorological conditions.     

Influence of the surface microlayer on atmospheric deposition of aerosols and polycyclic aromatic hydrocarbons

Atmospheric dry deposition is an important process for the introduction of aerosols and pollutants to aquatic environments. The objective of this paper is to assess, for the first time, the influence that the aquatic surface microlayer plays as a modifying factor of the magnitude of dry aerosol deposition fluxes. The occurrence of a low surface tension (ST) or a hydrophobic surface microlayer has been generated by spiking milli-Q water or pre-filtered seawater with a surfactant or octanol, respectively. The results show that fine mode (<2.7 μm) aerosol phase PAHs deposit with fluxes 2–3 fold higher when there is a low ST aquatic surface due to enhanced sequestration of colliding particles at the surface. Conversely, for PAHs bound to coarse mode aerosols (>2.7 μm), even though there is an enhanced deposition due to the surface microlayer for some sampling periods, the effect is not observed consistently. This is due to the importance of gravitational settling for large aerosols, rendering a lower influence of the aquatic surface on dry deposition fluxes. ST (mN m⁻¹) is identified as one of the key factor driving the magnitude of PAH dry deposition fluxes (ng m⁻² d⁻¹) by its influence on PAH concentrations in deposited aerosols and deposition velocities (v_d, cm s⁻¹). Indeed, v_d values are a function of ST as obtained by least square fitting and given by Ln(v_d)=−1.77 Ln(ST)+5.74 (r²=0.95) under low wind speed (average 4 m s⁻¹) conditions.     

Atmospheric concentrations of ammonia and ammonium at an agricultural site in the southeast United States

In this study, we present ∼1 yr (October 1998–September 1999) of 12-hour mean ammonia (NH₃), ammonium (NH₄⁺), hydrochloric acid (HCl), chloride (Cl⁻), nitrate (NO₃⁻), nitric acid (HNO₃), nitrous acid (HONO), sulfate (SO₄²⁻), and sulfur dioxide (SO₂) concentrations measured at an agricultural site in North Carolina's Coastal Plain region. Mean gas concentrations were 0.46, 1.21, 0.54, 5.55, and 4.15 μg m⁻³ for HCl, HNO₃, HONO, NH₃, and SO₂, respectively. Mean aerosol concentrations were 1.44, 1.23, 0.08, and 3.37 μg m⁻³ for NH₄⁺, NO₃⁻, Cl⁻, and SO₄²⁻, respectively. Ammonia, NH₄⁺, HNO₃, and SO₄²⁻ exhibit higher concentrations during the summer, while higher SO₂ concentrations occur during winter. A meteorology-based multivariate regression model using temperature, wind speed, and wind direction explains 76% of the variation in 12-hour mean NH₃ concentrations (n=601). Ammonia concentration increases exponentially with temperature, which explains the majority of variation (54%) in 12-hour mean NH₃ concentrations. Dependence of NH₃ concentration on wind direction suggests a local source influence. Ammonia accounts for >70% of NH_x (NH_x=NH₃+NH₄⁺) during all seasons. Ammonium nitrate and sulfate aerosol formation does not appear to be NH₃ limited. Sulfate is primarily associated ammonium sulfate, rather than bisulfate, except during the winter when the ratio of NO₃⁻–NH₄⁺ is ∼0.66. The annual average NO₃⁻–NH₄⁺ ratio is ∼0.25.