Dry Deposition Monitoring in Europe

Between 1993 and 1999 two EU funded projects wereexecuted aimed at (i) the development of drydeposition monitoring methods for core sites andlarge scale application, (ii) the installation andrunning of three core sites in Europe and (iii) the improvement and validation of models used forregional application. This article provides anoverview of the development of depositionmonitoring stations and the main results of thethree core sites, which were operated between1995 and 1998. Furthermore, the results of thedevelopment of a low cost monitoring system arepresented. Continuous measurements were made ofboth wet and dry deposition of sulphur andnitrogen components and base cations. The 4 yearsof data show a decrease in sulphur loads and notrend for the other components. It is shown thatthe surface affinities for sulphur depositionalso changed during the years, underpinning theneed for dry deposition monitoring. A conditionaltime average gradient system was successfullydeveloped and tested and provides a good meansfor low cost monitoring of dry deposition fluxes.The costs can be reduced by a factor of 3–4 without losing the accuracy of the annual average gas fluxes.     

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.     

Deposition Velocities of SO2 and O3 over Agricultural and Forest Ecosystems

The results of field studies that measured the flux anddeposition velocity of SO₂ and O₃ are reported. Three of the studies were over agricultural crops (pasture, corn, and soybean), and two were over forest (a deciduous forest and a mixed coniferous–deciduous forest). In all cases the deposition velocity for SO₂ was higher than that for O₃. Diurnal cycles of SO₂ deposition velocity were similar in shape, but not magnitude for all surfaces; however those for O₃ showed some difference between forest sites where the peak was in the morning, and the agricultural sites where the peak occurred at mid-day. Seasonal cycles of SO₂ were affected by deposition to surfaces when leaves were not active, yet surface conductance is significant, but not for O₃ where stomatal uptake is the primary pathway for deposition.(On assignment to the National Exposure Research Lab., US EPA) (e-mail:     

Atmospheric Deposition of Reactive Nitrogen on Turf Grassland in Central Japan: Comparison of the Contribution of Wet and Dry Deposition

The atmospheric deposition of reactive nitrogen on turf grassland in Tsukuba, central Japan, was investigated from July 2003 to December 2004. The target components were ammonium, nitrate, and nitrite ions for wet deposition and gaseous ammonia, nitric and nitrous acids, and particulate ammonium, nitrate, and nitrite for dry deposition. Organic nitrogen was also evaluated by subtracting the amount of inorganic nitrogen from total nitrogen. A wet-only sampler and filter holders were used to collect precipitation and the atmospheric components, respectively. An inferential method was applied to calculate the dry deposition velocity of gases and particles, which involved the effects of surface wetness and ammonia volatilization through stomata on the dry deposition velocity. The mean fraction of the monthly wet to total deposition was different among chemical species; 37, 77, and 1% for ammoniacal, nitrate-, and nitrite-nitrogen, respectively. The annual deposition of inorganic nitrogen in 2004 was 47 and 48 mmol m⁻² yr⁻¹ for wet and dry deposition, respectively; 51% of atmospheric deposition was contributed by dry deposition. The annual wet deposition in 2004 was 20, 27, and 0.07 mmol m⁻² yr⁻¹, and the annual dry deposition in 2004 was 35, 7.4, and 5.4 mmol m⁻² yr⁻¹ for ammoniacal, nitrate-, and nitrite-nitrogen, respectively. Ammoniacal nitrogen was the most important reactive nitrogen because of its remarkable contribution to both wet and dry deposition. The median ratio of the organic nitrogen concentration to total nitrogen was 9.8, 17, and 15% for precipitation, gases, and particles, respectively.     

Using Meteorological Model Output as a Surrogate for On-Site Observations to Predict Deposition Velocity

The National Oceanic and Atmospheric Administration's Multi-Layer Model (NOAA-MLM) is used by several operational dry deposition networks for estimating the deposition velocity of O₃, SO₂, HNO₃, and particles. The NOAA-MLM requires hourly values of meteorological variables. Since collection of on-site meteorology can be expensive, a study was performed to compare NOAA-MLM predicted deposition velocitiesusing modeled meteorological data in lieu of on-site meteorological data. NOAA-MLM was run for three sites in the Clean Air Status and Trends Network using on-site data as well as the output of two mesoscale meteorological models, Eta and MM5. The differences between the deposition velocities predictedusing the mesoscale models and those predicted using the on-sitemeteorological measurements ranged from –0.001 to 0.106 cm s^-1 and were within the model error determined in NOAA-MLM evaluation studies. This research shows that the NOAA-MLM is particularly sensitive to differences in atmospheric turbulence,soil moisture budget, and canopy wetness.(On assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina.) (author for correspondence, e-mail     

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.     

Correction Factors for Covariance between Concentration and Deposition Velocity on CASTNes HNO3 Deposition Estimates

The covariance between hourly concentration (C) and depositionvelocity (V) for various atmospheric species may act to bias the dry deposition (D) computed from the product of the weeklyaverage C and V. This is a potential problem for the CASTNet filter pack (FP) species, nitric acid (HNO₃). Using ozone (O₃) behavior as a surrogate for HNO₃, correctionfactors (CF) are developed to estimate this bias. Weekly CF for O₃ depend on both site and season, and seasonal average weekly CF for O₃ at a given site may be as high as 1.25.The seasonal magnitude of this CF is generally largest in summerand is ordered: summer fall spring > winter. The CF is drivento a large extent by the diurnal correlation between C andV (i.e., both are generally higher during the day and lower at night). However, since the diurnal C profile at elevated sites is relatively constant, the resulting correlation between C and V is small, and the CF at montane sites is generally negligiblysmall. The sampling protocol using daytime integrated sampling for a week and nighttime integrated sampling for a week capturesthe diurnal correlation between C and V adequately and may be used to aggregate relatively unbiased weekly D estimates. Day-night CF for O₃ are close to unity, and limited results suggest similar behavior for HNO₃. Using these limited FP results, the site- and seasonally-specific weekly CF forO₃are refined to estimate the corresponding CF for HNO₃. Worst-case adjustments for HNO₃ as high as 30% are indicated for summer periods at a given site.     

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.     

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.     

Aerosol Number Concentrations during Kosa Events on Suburban Hills in Japan

Measurements of aerosol size-separated number concentrations were performed in March 2001 on the Tama Hills of Japan, located near regions of heavy industry. The concentrations of particles larger than 1.0 μ m in diameter dramatically increased during the Kosa phenomena on 6–8 and 18–24 March. The number concentrations of coarse particles (> 3.0 μm) showed distinct diurnal variations, especially during the Kosa events. Fine particles smaller than 0.5 μm increased when the relative humidity was high and the wind speed was low. On the other hand, the coarse particles concentrations were well correlated with wind speed and temperature. The dry deposition velocity of the coarse particles at the forest canopy was estimated from the nighttime decrease in the number concentrations.     

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.     

Deposition and Storage of Spheroidal Carbonaceous Fly-Ash Particles in European Mountain Lake Sediments and Catchment Soils

Spheroidal carbonaceous particles(SCPs) are produced only from high temperaturecombustion of fossil-fuels. In mountain lakesystems, they provide an unambiguous indicator ofatmospheric deposition. In order to comparedepositional fluxes of SCPs between mountainareas experiencing various pollutant regimes,intensive bulk deposition sampling was undertakenat five sites across Europe. Catchment soil coresand lake sediment cores were also taken at eachsite to compare SCP storage over the post-industrial period. Atmospheric, sediment and soilSCP data showed similar patterns. Highestcontamination was found in Scotland, Slovakia andSpain with the Austrian site intermediate and themid-Norwegian site least contaminated. A highproportion of accumulated SCPs were found to bestored in catchment soils at each site.Therefore, a significant increase in soilerosion, possibly as a result of future climatechange, could lead to the input of largequantities of catchment stored SCPs and, byimplication, other atmospherically depositedcontaminants to the lake ecosystem.     

Implications of Heterogeneous Chemistry of Nitric Acid for Nitrogen Deposition to Marine Ecosystems: Observations and Modeling

Size resolved particle composition and nitric acid (HNO₃)measurements from the ASEPS'98 experiment conducted in the BalticSea are used to provide observational evidence of substantialgas-particle transfer of oxidized nitrogen (N) compounds in themarine boundary layer. We then focus on the importance ofHNO₃ reactions on sea salt particles in determining spatio-temporal patterns of N dry deposition to marine ecosystems.Modelling results obtained assuming no kinetic or chemical limiton HNO₃ uptake and horizontally homogeneous conditions withnear-neutral stability, indicate that for wind speeds 3.5 – 10 ms^-1 transfer of HNO₃ to the particle phase to formparticle nitrate (NO₃ ^-) may decrease the N depositionvelocity by 50%. We extend this research using the CHEM-COASTmodel to demonstrate that, in a sulphur poor environment undermoderate wind speeds with HNO₃ concentrations representativeof those found in the marine boundary layer, inclusion ofheterogeneous reactions on sea spray significantly reducesmodelled NO₃ ^- deposition in the near coastal zone.     

CHEMIFOG_V – A Model to Simulate Radiation Fogs and their Interaction with Vegetation and Chemistry

Radiation fog is an important modifier of atmosphericcompounds in the planetary boundary layer. In vegetated areas effects are especially pronounced due to the enlarged surface area. Besides affectingthe lower boundary of atmospheric models fog acts as amulti-phase reaction chamber leading to acid deposition. Here we present the 1-dimensional radiation fog modelCHEMIFOG_V to simulate regional radiation fogevents. The key feature of the fog model is thedetailed microphysics, where the aerosol/dropletspectrum is describedwith a joint 2-dimensional distribution, but also thedynamics, thermodynamics, and radiative transfer are calculated. Toinvestigate the interaction between fog and the biosphere amulti-layer vegetation module, including a soil module as well as a drydeposition module were coupled. Vegetation influences thedynamics, thermodynamics, and the radiation field of the lowestatmospheric layers. With CHEMIFOG_V, numerical case studieson dry and moist deposition processes on vegetation surfaces wereperformed. Hereby multi-phase chemistry and the processing of aerosolswere considered. The results show that the chemical composition of thedeposited fog droplets is mainly determined by the aerosol composition. Dry deposition fluxes are dependent on the incoming radiation and the leaves' surface conditions with respect to water coverage.Due to chemical aerosol processing and deposition, the aerosol spectrumis significantly modified in the planetary boundary layer.     

A Coupled Land-Surface and Dry Deposition Model and Comparison to Field Measurements of Surface Heat,Moisture, and Ozone Fluxes

We have developed a coupled land-surface and drydeposition model for realistic treatment of surface fluxes ofheat, moisture, and chemical dry deposition within acomprehensive air quality modelling system. A new land-surfacemodel (LSM) with explicit treatment of soil moisture andevapotranspiration and an indirect soil moisture nudging schemehas been added to a mesoscale meteorology model. The new drydeposition model uses the same aerodynamic and bulk stomatalresistances computed for evapotranspiration in the LSM. Thisprovides consistent land-surface and boundary layer propertiesacross the meteorological and chemical components of the system. The coupled dry deposition model also has the advantage of beingable to respond to changing soil moisture and vegetationconditions. Modelled surface fluxes of sensible and latent heatas well as ozone dry deposition velocities were compared to twofield experiments: a soybean field in Kentucky during summer 1995and a mixed forest in the Adirondacks of New York in July 1998.(on assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency) (author for correspondence, e-mail(on assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency)     

Evaluation and Improvement of a Dry Deposition Model using SO2 and O3 Measurements over a Mixed Forest

A dry deposition model (RDM) for operational application has beenevaluated and modified in the present study. Field measurements of friction velocity and dry deposition velocity of SO₂ andO₃ over a mixed forest have been used to evaluate RDM. It was found that RDM predicts friction velocities very close to measurements and thus it can predict reasonable aerodynamic resistance. RDM overestimated O₃ deposition during dry nighttime conditions and underestimated both O₃ andSO₂deposition for early morning hours. It could not predict the mean diurnal variation in deposition velocity for either O₃ or SO₂ deposition under wet surface conditions. Modifications have been made for O₃ and SO₂ dry deposition based on the comparison of results and based upon additional published data. Compared to an earlier version of RDM, the modified versionpredicts better results for O₃ and SO₂ dry deposition,especially under rain and dew conditions.     

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.     

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.     

Comparison of the Chemical Composition of Mineral Particles Collected in Dunhuang,China and those Collected in the Free Troposphere over Japan: Possible Chemical Modification during Long-Range Transport

The Asian continent is recognized as one of the most important sources of mineral (or soil) particles. These particles have a large potential to effect global changes through the biogeochemical cycle of particulates and through radiative balance (IPCC Third Assessment Report, 2001). Therefore, comparison of particle compositions near the source region and those after long-range transport is important in understanding the long-range particle transport phenomenon. Individual aerosolparticles were collected in Dunhuang (40°09N; 94°41E), China. Particles were collected at the campus of the Meteorological Bureau of Dunhuang City (17 August 2001) and near the Mogao Grots, located approximately 30 km from Dunhuang (18 August 2001, 18 October 2001 and 13 January 2002) using a two-stage low-volume impactor. The morphology of individual aerosol particles and their elemental compositions were examined via a scanning electron microscope (Hitachi, S-3000N) equipped with an energy dispersive X-ray (EDX) analyzer (Horiba, EMAX-500). The particles collected at these locations were comprised primarily of minerals, with the exception of sulphateparticles in the submicron range that were contained in thesample collected on 18 October 2001 (likely, ammonium sulphate). The most abundant elements were found to be Si and Al. Approximately 46–77% of the collected particles were Si-richparticles (composed primarily of quartz and aluminosilicate),and 13–41% of the collected particles were Ca-rich particles,such as calcite (CaCO₃), dolomite (CaMg(CO₃)₂),and gypsum (CaSO₄2H₂O). The fractions of Fe-rich, Mg-rich, Ti-rich, K-rich, and Cl-rich were 3–10, 0–7, 0–3, 0–1, and 0–1%, respectively. Similar types of mineral particles were found in the free troposphere over Japan(Trochkine et al., 2002). A number of differences were found to exist between the particles collected in China and thosecollected in Japan, and these differences can be explained bychemical modification of the particles during transport fromChina to Japan.     

A Chronology of Nitrogen Deposition in the UK Between 1900 and 2000

Measurements of the concentrations of nitrogen compounds in air and precipitation in the UK have been made since the mid-19th century, but no networks operating to common protocols and having traceable analytical procedures were established until the 1950s. From 1986 onwards, a high-quality network of sampling stations for precipitation chemistry was established across the UK. In the following decade, monitoring networks provided measurement of NO₂, NH₃, HNO₃ and a satisfactory understanding of the dry deposition process for these gases allowed dry deposition to be quantified. Maps of N deposition for oxidized and reduced compounds at a spatial scale of 5 km × 5 km are available from 1986 to 2000. Between 1950 and 1985, the more limited measurements, beginning with those of the European Air Chemistry Network (EACN) provide a reasonable basis to estimate wet deposition of NO ₃ ^– –N and NH ₄ ⁺ –N. For the first half of the century, estimates of deposition were scaled with emissions assuming a constant relationship between emission and deposition for each of the components of the wet and dry deposition budget at the country scale. Emissions of oxidized N, which dominated total nitrogen emissions throughout the century, increased from 312 kt N annually in 1900 to a peak of 787 kt for the decade 1980–1990 and then declined to 460 kt in 2000. Emissions of reduced N, largely from coal combustion were about 168 kt N in 1900, increasing to a peak of 263 kt N in 2000 and by now dominated by agricultural sources. Reduced N dominated the deposition budget at the country scale, increasing from 163 kt N in 1900 to 211 kt N in 2000, while deposition of oxidized N was 66 kt N in 1900 and 191 kt N in 2000. Over the century, 68 Mt (Tg) of fixed N was emitted within the UK, 78% as NO _x , while 29 Mt of nitrogen was deposited (43% of emissions), equivalent to 1.2 t N ha^–1, on average, with 60% in the reduced form. Deposition to semi-natural ecosystems is approximately 15 Tg N, equivalent to between 1 and 5 t N ha^–1, over the century and appears to be accumulating in soil. The N deposition over the century is similar in magnitude to the total soil N inventory in surface horizons.