The Control of SO2 Dry Deposition on to Natural Surfaces by NH3 and its Effects on Regional Deposition

Two years of continuous measurements of SO₂deposition fluxes to moorland vegetation are reported. The mean flux of 2.8 ng SO₂ m^-2 s^-1 is regulated predominantly by surface resistance (r _c) which, even for wet surfaces, was seldom smaller than 100 s m^-1. The control of surface resistance is shown to be regulated by the ratio of NH₃SO₂ concentrations with an excess of NH₃ generating the small surface resistances for SO₂. A dynamic surface chemistry model is used to simulate the effects of NH₃ on SO₂ deposition flux and is able to capture responses to short-term changes in ambient concentrations of SO₂, NH₃ and meteorological conditions. The coupling between surface resistance and NH₃/SO₂ concentration ratios shows that the deposition velocity for SO₂ is regulated by the regional pollution climate. Recent long-term SO₂ flux measurements in a transect over Europe demonstrate the close link between NH₃/SO₂ concentrations and rc (SO₂). The deposition velocity for SO₂ is predicted to have increased with time since the 1970s and imply a 40% increase in v _d at a site at which the annual mean ambient SO₂ concentrations declined from 47 to 3 g m^-3 between 1973 and 1998.     

Quantifying dry NH3 deposition to an ombrotrophic bog from an automated NH3 field release system

Providing an accurate estimate of the dry component of N deposition to low N background, semi-natural habitats, such as bogs and upland moors dominated by Calluna vulgaris is difficult, but essential to relate nitrogen deposition to effects in these communities. To quantify the effects of NH₃ inputs to moorland vegetation growing on a bog at a field scale, a field release NH₃ fumigation system was established at Whim Moss (Scottish Borders) in 2002. Gaseous NH₃ from a line source was released along of a 60 m transect, when meteorological conditions (wind speed >2.5 m s^–1 and wind direction in the sector 180–215°) were met, thereby providing a profile of decreasing NH₃ concentration with distance from the source. In a complementary study, using a NH₃ flux chamber system, the relationships between NH₃ concentrations and cuticular resistances were quantified for a range of NH₃ concentrations and micrometeorological conditions for moorland vegetation. Cuticular resistances increased with NH₃ concentration from 11 s m^–1 at 3.0 g m^–3 to 30 s m^–1 at 30 g m^–3. The NH₃ concentration data and the concentration-dependent canopy resistance are used to calculate NH₃ deposition taking into account leaf surface wetness. The implications of using an NH₃ concentration-dependent cuticular resistance and the importance for refining critical loads are discussed.     

Characteristics of an Ozone Deposition Module

An ozone deposition module is being developed to allow the estimation of stomatal fluxes of ozone into a number of vegetation types. This model is designed to be linked into a regional chemical-transport model for use within the European Monitoring and Evaluation Programme (EMEP), to provide information on possible risks to vegetation across Europe. This paper investigates some characteristics of this deposition module, for sites in very different climate zones. The model results suggest that both stomatal and non-stomatal fluxes are comparable in magnitude.     

Ozone Dry Deposition Velocities for Coastal Waters

Air-sea exchange rates for ozone were measured by the eddy correlation technique at a site on the north Norfolk coast in the UK. The average surface resistance to ozone uptake was found to be, r_s(O₃) = 1,000 ± 100 s m^-1. Micrometeorological measurements of trace gas fluxes to ocean surfaces are rare but a review of available measurements suggests that we can constrain sea water surface resistance for ozone to between 1,000 (Regener (1974), and this work) and 1,890 s m^-1 (Lenschow et al., 1982), yielding surface deposition velocities between 0.53 and 1.0 mm s^-1. These values are more than an order of magnitude greater than can be explained by laboratory determined mass accommodation coefficients for ozone to water. The importance of dry deposition with respect to process air-sea exchange models is highlighted. A trend in surface deposition velocity with wind speed was also observed supporting a surface chemical enhancement mechanism of ozone uptake which in turn is enhanced by near surface mixing processes.     

Comparisons of Measured and Modelled Ozone Deposition to Forests in Northern Europe

The performance of a new dry deposition module, developedfor the European-scale mapping and modelling of ozone flux to vegetation, was tested against micrometeorological ozone and water vapour flux measurements. The measurement data are for twoconiferous (Scots pine in Finland, Norway spruce in Denmark) and one deciduous forest (mountain birch in Finland). On average, themodel performs well for the Scots pine forest, if local inputdata are used. The daytime deposition rates are somewhat over-predicted at the Danish site, especially in the afternoon. The mountain birch data indicate that the generic parameterisationof stomatal responses is not very representative of this northernspecies. The module was also tested by using modelled meteorological data that constitute the input for a photochemical transport model.     

Effects of Soil Moisture Variations on Deposition Velocities Above Vegetation

The parameterized subgrid-scale surface flux (PASS) modelprovides a simplified means of using remote sensing data from satellites and limited surface meteorological information to estimate the influence of soil moisture on bulk canopy stomatalresistances to the uptake of gases over extended areas.PASS-generated estimates of bulk canopy stomatal resistance were usedin a dry deposition module to compute gas deposition velocitieswith a horizontal resolution of 200 m for approximately 5000 km² of agricultural crops and rangeland. Results were compared with measurements of O₃ flux and concentrations made during April and May 1997 at two surface stations and from an aircraft. The trend in simulated O₃ deposition velocityduring soil moisture drydown over a period of a few days matchedthe trend observed at the two surface stations. For areas underthe aircraft flight paths, the variability in simulated O₃ deposition velocity was substantially smaller than the observedvariability, while the averages over tens of kilometers were usually in agreement within 0.1 cm s^-1. Model results indicated that soil moisture can have a major role in depositionof O₃ and other substances strongly affected by canopy stomatal resistance.     

An Automated Wet Deposition System to Compare the Effects of Reduced and Oxidised N on Ombrotrophic Bog Species: Practical Considerations

Critical N loads for ombrotrophic bogs, which often contain rare and N-sensitive plants (especially those in lower plant groups: lichens, mosses and liverworts), are based on very few experimental data from measured, low background N deposition areas. Additionally the relative effects of reduced versus oxidised N are largely unknown. This paper describes an automated field exposure system (30 km S. of Edinburgh, Scotland) for treating ombrotrophic bog vegetation with fine droplets of oxidised N (NaNO₃) and reduced N (NH₄Cl). Whim Moss exists in an area of low ambient N deposition (ca. 8 kg N ha^–1 y^–1), the sources and quantification of which are described. The wet N treatment system is run continuously, and is controlled/activated by wind speed and rainfall to provide a unique simulation of real world treatment patterns (no rain=no treatment). Simulated precipitation is supplied at ionic concentrations below4mMin rainwater collected on site. Treatments provide a replicated dose response to 16, 32 and 64 kg N ha^–1 y^–1 adjusted for ambient deposition (8 kg N ha^–1 y^–1). The 16 and 64 kg N ha^–1 y^–1 are duplicated with a P+K supplement. Baseline soil chemistry and foliar nutrient status was established for all 44 plots for Calluna vulgaris, Sphagnum capillifolium, Hypnum jutlandicum and Cladonia portentosa.     

Experimental Assessment of Atmospheric Ammonia Dispersion and Short Range Dry Deposition in a Maize Canopy

In order to study the effect of thevegetation structure on atmospheric ammonia(NH₃) dispersion and deposition, anexperiment was set up near Paris, in July 1997.Between 12 and 162 m downwind of a 200 m line-source releasing 600 to 1200 g NH₃hr^-1placed at the top of a maize canopy, NH₃concentration was measured, within and above thecanopy, with a set of 30 active, acid-coateddenuders over periods of 2 to 3 hr. Eight datasets were collected over a one-month period.NH₃ concentration decreased sharply withdistance to the source, from up to800 g NH₃ m^-3 at 12 m, to lessthan 10 g NH₃ m^-3 at 162 m andshowed strong vertical gradients. Within thecanopy, the concentration scaled using thefriction velocity, the canopy height, and thesource strength, exhibited a universal power lawrelationship as a function of the normaliseddownwind distance from the source. A mass balancemethod and a resistance model approach were usedas independent estimates of the cumulateddeposition at 162 m downwind from the source,which range between 1 and 29% of the emittedNH₃. Both methods agreed approximately inmagnitude. A sensitivity analysis showed that thecuticular uptake and the compensation point aremajor parameters that needs to be bettercharacterised under high NH₃ concentrationif one wants to improve NH₃ short-rangedeposition modelling.     

Formation of Reactive Gaseous Mercury in the Arctic: Evidence of Oxidation of Hg° to Gas-Phase Hg-II Compounds after Arctic Sunrise

We have measured total gaseous mercury concentrations(Hg°) at Point Barrow, Alaska since September 1998 in aneffort to determine the geographic extent and reaction mechanismof the so-called mercury depletion events (MDE) previouslyreported in the high Arctic at Alert, Canada. Hg° has beensampled now for nearly 2 years at Barrow. In September, 1999, webegan making the first automated measurements of reactive gaseousmercury (RGM) attempted in the Arctic, along with measurements ofHg accumulation in snowpack to determine the fate of the depleted Hg°. During the fall and early winter, Hg°and RGM exhibit only minor variation, Hg° remaining within10% of global background, near 1.6–1.8 ng m^-3. The MDEperiods are quite different, however; within days of Arcticsunrise in January, Hg° exhibits major variations from themean, rapidly dropping as low as 0.05 ng m^-3 and then cyclingback to typical levels, sometimes exceeding global background. These events continue throughout Arctic spring, then end abruptlyfollowing snowmelt, in early June. Prior to Arctic sunrise, RGMremains near detection (<2 pg m^-3), but after sunriseincreases dramatically (to levels as high as 900 pg/m³) insynchrony with the depletion of Hg°. Both phenomenaexhibit a strong diel cycle, in parallel with UV-B. We concludethat MDE's involve rapid in-air oxidation of Hg° to aspecies of RGM by photochemically-driven reactions, probablyinvolving the same reactive bromine and chlorine compoundsinvolved in ozone destruction. Sharp increases in Hg in thesurface snowpack after sunrise coincident with periods of peakRGM suggest surface accumulation of the RGM by dry deposition.     

Winter and Spring Thaw Measurements of N2O,NO and NOx Fluxes using a Micrometeorological Method

The impact of nitrogen fertilizers on gaseous emissions duringwinter and spring-thaw is not well understood and was the objective of this research. Using a micrometeorological method,N₂O, NO and NO_x fluxes from ryegrass were measured from November 1997 to March 1998. Three different mineralfertilizers were applied in November: urea (U), slow-release urea(SRU) and ammonium nitrate (AN). N₂O emissions during the winter were small, increasing significantly in March. Total losses of N₂O-N were significantly higher from SRU and U plots, with winter N₂O emissions accounting for 50% of annual losses. Nitric oxide fluxes from all plots weresmall during the measurement period (<0.9 ng N m^-2 s^-1). The NO fluxes from U and AN fertilized plots were significantly higher than from SRU and control plots. NO₂ fluxes were always negative (–6 ng N m^-2 s^-1)indicating deposition, but decreased to –2 ng N m^-2s^-1 when snow was present on the soil surface. Our resultsindicate that the form of inorganic N applied has an effect on NO+ N₂O emissions but not on NO₂ fluxes.Sponsored by CAPES – Brasília, Brazil     

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.     

Ozone Deposition to a Coniferous and Deciduous Forest in the Czech Republic

Estimates of ozone concentration and deposition flux to coniferous and deciduous forest in the Czech Republic on a 1 × 1 km grid during growing season (April–September) of the year 2001 are presented. Ozone deposition flux was derived from ozone concentrations in the atmosphere and from its deposition velocities. To quantify the spatial pattern in surface concentrations at 1 km resolution incorporating topography, empirical methods are used. The procedure maps ozone concentrations from the period of the day when measurements are representative for the forest areas of countryside. The effects of boundary layer stability are quantified using the observed relationship between the diurnal variability of surface ozone concentration and altitude. Ozone deposition velocities were calculated according to a multiple resistance model incorporating aerodynamic resistance (R _a ), laminar layer resistance (R _b ) and surface resistance (R _c ). Surface resistance (R _c ) comprises stomatal resistance (R _sto ). R _sto was calculated with respect to global radiation, surface air temperature and land cover. Modelled total and stomatal ozone fluxes are compared with the maps describing equivalent values of AOT40 (accumulated exposure over threshold of 40 ppb). For forests, the critical level (9,000 ppbh May–July daylight hours) is exceeded over 50% of forested territory. This indicates the potential for effects on large areas of forest. There is significiant correspondence between the exposure index AOT40 and the total ozone flux, but the relation between the total ozone flux and AOT40 exposure index is not clear in all parts of the forest territory.     

Changes in Atmospheric Deposition Rates of Heavy Metals in Sweden A Summary of Nationwide Swedish Surveys in 1968/70 – 1995

The Swedish nationwide surveys of atmospheric heavy metal deposition in 1968/70 – 1995 using bryophytes (carpet-forming mosses) as monitors are reviewed. Considered are cadmium (Cd), copper (Cu), iron (Fe), lead (Pb), mercury (Hg), nickel (Ni), vanadium (V), and zinc (Zn). The close agreement between data obtained with deposition (precipitation) collectors and moss carpet analysis is documented briefly, as well as measures of quality control and assessment of reproducibility. Since 1968/70, the deposition rate of the heavy metals considered has declined gradually and evenly, particularly in the southern parts of the country, reflecting an improvement of general air quality due to decreasing dust emission from mainly industry and fossil fuel combustion in northern and western Europe. By far the greatest absolute decrease in deposition rate was measured in Fe, which is a main constituent of most man-generated dust particles. However, the greatest per cent decreases in deposition rates were measured for Pb. The Pb concentration of moss carpets in Sweden as a whole in 1995 was only 11% of the value in 1968/70. Corresponding figures for Fe was 20%, Cd 24%, Ni 28%, Hg 31%, V 43%, Zn 51%, and Cu 52%. For Zn the current deposition rate seems to approach a natural baseline, whereas deposition of the other seven elements are still decreasing according to the surveys of 1990 and 1995.     

The Influence of Atmospheric N Deposition on Nitrous Oxide and Nitric Oxide Fluxes and Soil Ammonium and Nitrate Concentrations

The deposition of atmospheric N to soils provides sources of available N to the nitrifying and denitrifying microbial community and subsequently influences the rate of NO and N₂O emissions from soil. We have investigated the influence of three different sources of enhanced N deposition on NO and N₂O emissions 1) elevated NH₃ deposition to woodlands downwind of poultry and pig farms, 2) increased wet cloud and occult N deposition to upland forest and moorland and 3) enhanced N deposition to trees as NO ₃ ^– and NH ₄ ⁺ aerosol. Flux measurements of NO and N₂O were made using static chambers in the field or intact and repacked soil cores in the laboratory and determination of N₂O by gas chromatography and of NO by chemiluminescence analysis. Rates of N deposition to our study sites were derived from modelled estimates of N deposition, NH₃ concentrations measured by passive diffusion and inference from measurements of the ²¹⁰Pb inventory of soils under tree canopies compared with open grassland. NO and N₂O emissions and KCl-extractable soil NH ₄ ⁺ and NO ₃ ^– concentrations all increased with increasing N deposition rate. The extent of increase did not appear to be influenced by the chemical form of the N deposited. Systems dominated by dry-deposited NH₃ downwind of intensive livestock farms or wet-deposited NH ₄ ⁺ and NO ₃ ^– in the upland regions of Britain resulted in approximately the same linear response. Emissions of NO and N₂O from these soils increased with both N deposition and KCl extractable NH ₄ ⁺ , but the relationship between NH ₄ ⁺ and N deposition (ln NH ₄ ⁺ = 0.62 ln N_deposition + 0.21, r ² = 0.33, n = 43) was more robust than the relationship between N deposition and soil NO and N₂O fluxes.     

Aerosol Particle Processing and Removal by Fogs: Observations in Chemically Heterogeneous Central California Radiation Fogs

Fog composition and deposition fluxes of fog waterand fog solutes were measured in six radiation fogevents in San Joaquin Valley, California duringwinter 1998/1999. Measurements made at 2 hrintervals with 0.30 m² and 0.06 m² Teflondeposition plates yielded excellent reproducibility(relative standard deviations of 3.8–6.0%) forwater, nitrate, sulfate and ammonium. Water fluxesmeasured at 5 min intervals with a recordingbalance agreed well with the deposition platemeasurements before 8:00 AM. After 8:00 AMevaporation proved problematic. The averagedeposition velocity from the study for fog nitrate(3.8 cm s^-1) was less than those for fogsulfate (5.1 cm s^-1) and ammonium (6.7 cms^-1). All three species generally exhibitedsmaller deposition velocities than fog water. Thespecies dependent trend in deposition velocitieswas consistent with preferential enrichment ofthese species in small fog drops (nitrate > sulfate> ammonium).     

A Relaxed Eddy Accumulation System for the Automated Measurement of Atmospheric Ammonia Fluxes

A continuous relaxed eddy accumulation system ispresented for the automated measurement of surface/atmosphere exchange fluxes of atmospheric ammonia (NH₃) at a single height. The new system features sampling by parallel plate denuder inlets, online chemical analysis using the conductivity cell of a commercially available NH₃ analyzer and online flux calculation. The effective detection limit of the system for air concentrations is 0.2 g m^-3 and it is estimated to resolve fluxes > ± 20 ng m^-2 s^-1, depending on the NH₃ concentration and turbulence. The performance of the system was tested in two measurement campaigns above agricultural grassland, in which it was compared with a 3-point continuous gradient system. During the first campaign, after urea application of 47 kg N ha^-1 in autumn, the REA system derived fluxes which were on average twice as large as the gradient fluxes, while concentrations agreed closely (on average within 4%). Possible reasons include differences in the footprint and an over-correction of the gradient flux in stable conditions. Due to wet and cold conditions, only 0.3% of the fertilizer N was volatilized as NH₃ during the first week. Results from the deployment of an improved system are presented for a summer day, 6 days after fertilization with calcium ammonium nitrate. The agreement of both concentrations (on average within 13%) and fluxes (26%) was very encouraging and similar to the agreement found between two state-of-the-art gradient systems with online analysis.     

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⁺].     

On the Size Dependence of Particle Deposition

Measurements of dry deposition ofparticles 0.1 to 1.0 m diameter to forest bythroughfall and eddy correlation methods giveresults of 1.0 cm s^-1 or more, whilemechanistic models do not explain values greaterthan about 1 mm s^-1. Results of othermethods involving radioactive tracers arerecalled. These data indicate values of about 5 mm s^-1. The possibility of additionalmechanisms, omitted from the models, is difficultto exclude, but much of the remaining discrepancymay be due to the wide size distribution of theadventitious radioactive tracers in the atmosphere.     

Integrated Nitrogen Modeling in a Boreal Forestry Dominated River Basin: N Fluxes and Retention in Lakes and Peatlands

Two models, N_EXRET and INCA, were applied to the Simojoki river basin (3160 km²) in northern Finland in order to assess nitrogen retention in wetlands and lakes. N_EXRET is a spatial, export coefficient-based N export and retention model developed for large river basins. It utilizes remote sensing-based land use and forest classification, evaluated export coefficients, and data on areal N deposition and point sources of N. A new version (v1.7) of the Integrated Nitrogen in CAtchments model (INCA) is a semi-distributed, dynamic nitrogen process model, which simulates and predicts nitrogen transport and processes within catchments. Average retention of the gross total N load of 700 t a^-1 to the river system was estimated using N_EXRET model as 17 t N a^-1 to the wetlands and 77 t N a^-1 to the lakes. A good fit was found between modeled and measured values along the river. Inorganic N fluxes simulated by the INCA model were compared with measured fluxes along the river Simojoki, with a good fit between modeled and measured NH₄ ⁺-N fluxes, and an adequate fit for NO₃ ^--N fluxes. Both fluxes were overestimated at the first reach, below Lake Simojärvi. High percentage of peatlands led to high NH₄ ⁺-N/NO₃ ^--N ratios derived from data, indicating negligible nitrification in large river subbasins and particularly in small research catchments.     

Deposition Loads of Sulphur and Nitrogen in Germany

High spatial resolution maps of deposition loads in Germanyare produced as an input for abatement strategy research andfor critical loads exceedance calculations on a nationalscale. In this paper methods ofmapping total deposition loads in Germany and preliminarymaps of nitrogen and sulphur deposition loads for the year1993 are presented. A comparison of these mapping resultswith EMEP deposition mapping results has been carried out.The differences in the results of the German national and theEuropean EMEP mapping, due to different databases anddifferent methods, are quantified and discussed. Highresolution maps of deposition loads are compared to Europeanlow resolution maps on the same temporal and spatial scale,assuming that on average both should lead to similar results.However, the average differencescalculated for 23 EMEP 150 × 150 km² grid cells over Germanywere found to be 33% higher for sulphur (S) total depositionby the German method 65% higher for S dry deposition and1% lower for S wet deposition. The German results fornitrogen (N) total deposition are 2% higher than the EMEPresult 22% higher for N dry deposition and 10% lower for Nwet deposition.