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.     

Air–Soil Exchange of NO,NO2 and O3 in Forests

The exchange of NO, NO₂ and O₃ at the soil surface wasmeasured with automatic dynamic chambers in a spruce forest and in abeech forest during periods of several months.NO was emitted from the soil at a rate of0–8 ng N m^-2 s^-1(spruce) and 0–15 ng Nm^-2 s^-1(beech), but there was no simple relationship between the flux andeither soil temperature or soil moisture. NO₂ and O₃ weredeposited at the soil surface. Deposition velocities forNO₂were on average 0.3 mm s^-1 (spruce) and 0.1 mms^-1(beech), and the deposition velocities of O₃ were on average 1.6 mm s^-1 (spruce) and 1.4 mm s^-1 (beech). The depositionvelocity of O₃ is fairly constant whereas the deposition velocityof NO₂ varies greatly, but the reasons remain to be investigated.     

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.     

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.     

Laboratory Measurement of Dry Deposition of Ozone onto Northern Chinese Soil Samples

We used laboratory experiments to investigate surface resistance (R _c) to dry deposition of ozone (O₃) on different types of soil samples collected from the arid deserts and the Loess Plateau of northern China. Furthermore, we measured the factors that affected R _c, which depends on the physical and chemical interaction between trace constituents and the deposition surface, and evaluated deposition velocity (V _d). There was little influence of geometric surface area, soil weight, or O₃ concentration on V _d of O₃. The effect of relative humidity (RH) (i.e. moisture content of the soil) on O₃ uptake was in agreement with results reported in the literature: a distinct RH dependence of V _d and little uptake under water-saturated conditions were observed. R _c values for all the soil samples examined were in the range 0.21–3.3 s mm⁻¹ and were exponentially related to the surface area of the particles and the organic carbon content of each soil sample at RH of both <10 and 60%.     

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⁺].     

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 μg m^?3 to 30 s m^?1 at 30 μg 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.     

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.     

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).     

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     

Metabolic and Environmental Control on Methane Emission from Soils: Mechanistic Studies of Mesotrophic Fen in West Siberia

The biological mechanisms regulating methane emission fromnatural wetlands are the focus of this article. A novel techniqueprovides estimates of the distribution of CH₄ sources withinan undisturbed soil profile by recording the transient gasdynamics after soil enclosure by deep (50 cm) chamber. Thecombined use of conventional surface and soil chambers across a200-m fen transect allowed us to relate the observed methaneemission to its instant generation and uptake. Surprisingly, themethane generation was relatively constant (9–12 mg CH₄-C hr^-1 m^-2) and highly variable net emission (0.2–20 mg CH₄-C hr^-1 m^-2) was closely correlated (r = –0.809)with methane uptake. In laboratory incubations, CH₄ uptakefollowed Michaelis-Menten kinetics. Added chloride and nitrateirrespective of the cation's nature suppressed uptake as a strongnoncompetitive inhibitors (K _i 0.5 mM). The methaneformation turned out to be unstable and under anaerobicincubation, the formation of CH₄, CO₂ andH₂displayed sustained weekly oscillations. We conclude that effectsof environmental factors alone are not sufficient topredict the variation in emission, which depends also on metabolic control of respective soil organisms. The multitude ofsuch controls is dependent on diversity of respective soilorganisms and could be grouped into a limited number ofcategories considerably simplifying large-scale simulations.     

Ozone Deposition at a Forest Site in NE Bavaria

The dry deposition of ozone to aconiferous forest in northeastern Bavaria(southern Germany) was quantified during 1999with both the eddy correlation method and a bigleaf model. The model included parameterizationsof the atmospheric transfer resistances fromdirect measurements, stomatal resistance from aplant ecological model, and an estimation of thecuticle resistance as function of leaf wetness.Early in the season, the measured and themodelled deposition fluxes were in goodagreement, although the modelled fluxes tended tounderestimate the measured ones. Thisunderestimation was more pronounced in the latesummer, when high nocturnal fluxes werefrequently measured. The model parameterizationof the cuticle and the stomatal resistances didnot allow for such high fluxes. In these cases,the 24 hour average of the measured fluxes wereup to 4.5 times higher than the modelled ones.The reasons for these large discrepancies remainunknown. However, assigning the unaccounted partof the deposition to a nonstomatal surfacedeposition pathway, a new parameterization of therespective resistance yielded an average value of300 s m^-1. It exhibited a decreasing trendthrough the vegetation period.     

Measuring eddy covariance fluxes of ammonia using tunable diode laser absorption spectroscopy

Field measurements of NH₃ fluxes using an eddy covariance technique were made for a total of 60 days between July and September 2002 at an intensively managed grassland in Southern Scotland. The collected data demonstrate the suitability of a tuneable diode laser absorption spectroscopy (TDLAS) system coupled with a sonic anemometer for eddy covariance measurements. The novelty of these measurements is the application to ammonia, which has only become measurable using TDLAS techniques recently, because of its small ambient concentration. Data presented in this paper show typical features of the fluxes and concentration for the summer season. NH₃ concentration and flux values are in a similar range to previous studies using flux gradient methods at the same field site, although the particularly wet season reduced the concentration of NH₃ in the air. For an example day, measured NH₃ fluxes ranged between ?11 and 44 ng m^?2 s^?1 with an average value of 3.78 ng m^?2 s^?1 indicating a small net emission from the vegetation. Spectral analysis executed on the data shows the percentage of flux carried by the small eddies (from 0.2 to 2 m) suggesting that high detection frequency instruments are particularly suitable for estimating NH₃ fluxes between atmosphere and vegetation.     

Fluxes and Loading of Heavy Metals, Benzo[a]pyrene and Oil Products in Vilnius City

The concentrations of heavy metals Pb, Cd, Cu, Zn and Hg, benzo[a]pyrene and oil products (C₁₅–C₂₈) in bulk (wet and dry) atmospheric deposition in Vilnius city in 2005–2006 were analysed. The highest flux to the ground surface of the city residential area, reaching 1,680 mg m^?2 year^?1, was determined for oil products, which in atmospheric bulk deposition was estimated to be mainly in the form of solid sediments. Among heavy metals, the highest flux was determined for Zn (113.5 mg m^?2 year^?1), while the lowest flux was determined for Hg (0.06 mg m^?2 year^?1). The flux of investigated pollutants ranges from a few times, or for some pollutants, up to one order of magnitude higher at the urban sampling site in comparison to residential or background sites. Some hundred tons of oil products, approximately 52 tons of zinc and a considerably lower amount of mercury, benzo[a]pyrene and cadmium deposit yearly to the ground and water surface of Vilnius city. Metallic constructions related to transport and buildings, automobile exhausts, spills of fuel and lubricants are suggested to be the factors which result in the accumulation of high amounts of heavy metals, oil products and other pollutants on the ground surface of the city.     

Air Pollution Zones and Harmful Pollution Levels of Alkaline Dust for Plants

For characterisation of landscapes in north-eastern Estoniaaffected by alkaline oil shale fly ash and cement dust the zonation-method based on average annual (C _y) and short-termconcentrations of pollutants in the air was used, as well as on deposition loads of dust and Ca²⁺. In the overground layer of atmosphere the zones with different air pollution loads were distinguished. A comparative analysis of pollution zones characteristics and biomonitoring data revealed that for sensitive lichen the dangerous level of alkaline dust in the air, introducingthe degradation of Sphagnum sp. at the level of C _y of dust 10–20 g m^-3 and at 0.5–1 hr maximums 100–150 g m^-3. For Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) this limited concentration (decline of growth parameters) of cement dust is correspondingly following: 30–50 g m^-3 and 150–500 g m^-3, in case of fly ash the limit level of C _y amounting 100 g m^-3. Daily deposition load of Ca²⁺ should not exceed approximately 4.5–15 mg m^-2 for lichen; for conifers the harmful pollution load is higher – >22 mg m^-2.     

Deposition and Fate of Lead in a Forested Catchment, Lesni Potok, Central Czech Republic

The deposition of trace elements and their fate in a forest ecosystemhas been monitored at the experimental site, Lesni Potok catchment (LP), with granite bedrock. The catchment is located 30 km ESE from Prague. Annual bulk Pb-deposition flux F_Pb was 3.41 kg km^-2 a^-1 in 1994 and gradually decreased to 0.49 kg km^-2 a^-1 in 2001. The decrease is comparable with those observed in Germany and in the U.S.A. in the 1970s and 1980s. The total sales ban of leaded gasoline in the Czech Republic since January 2001 was accompanied by a pronounced decrease of F_Pb in a single year. The residual Pb-deposition flux is assigned to both the long-range transport of fine-grained vehicular lead aerosol (with a long residence time in the atmosphere) and to theemissions from power plant boilers burning lignite mined in the Czech northwest coal basin. The F_Pb of lead correlates stronglywith those of As, Cd, Cu, Zn and Be, the typical metals in coal fly ash, at two monitored sites. Topsoil horizons contain elevated concentrations of Pb (53–67 mg kg^-1), which are of anthropogenicorigin. Soils in the riparian areas contain increased concentrations of Pb when compared to soils on the hillslope areas. Significant amounts of Pb were found on a stream substrate and Fe-precipitate sampled from the stream. Low concentrations of Pb in bark and bole wood suggest that the uptake of Pb by vegetation is negligible. The very small surface water outputs (average of 0.002 kg km^-2 a^-1) compared to inputs (average of 1.890 kg km^-2 a^-1) from the LP catchment indicate an ongoing accumulation of Pb in a forested landscape.     

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.     

Fluxes of NO3-, NH4+, NO,NO2, and N2O in an Old Danish Beech Forest

The fluxes of the major nitrogen compounds havebeen investigated in many ecosystem studies over the world.However, only in few studies has attention been drawn to theimportance of the fluxes of minor gaseous nitrogen compoundsto complete the nitrogen cycle. In Denmark a detailed study onthe nitrogen cycle in an old beech forest has been implementedin 1997 at Gyrstinge near Sorø, Zealand. The study includesthe fluxes of the gases NO, N₂O and water mediatedtransport of NO₃ ^- and NH₄ ⁺. Measurementsof the fluxes of the gaseous compounds are performed withmicro-meteorological methods (eddy-correlation and gradient)and with chambers. Water mediated fluxes encompass rain,throughfall, stem-flow and leaching from the root zone. Thehydrological model is verified by TDR measurements. The findings show that the total water mediated N input tothe forest floor with throughfall and stemflow was 25.6 kg Nha^-1 yr ^-1, and open field wet deposition withprecipitation was 19.0 kg N ha^-1 yr ^-1. The internalcycling of N in the ecosystem measured as turnover oflitterfall and plant uptake was 100 kg N ha^-1 yr ^-1and 14 kg N ha^-1 yr ^-1, respectively. The fluxes ofthe gaseous N compounds NO and N₂O were of minorimportance for the total N turnover in the forest, NO_xemission being <1 kg N ha^-1 yr ^-1 and N₂Oemission from the soil being 0.5 kg N ha^-1 yr ^-1 withno significant difference between wet and dry soils.Concentrations of NO₃ ^- and NH₄ ⁺ in thesoil solution beneath the rooting zone are very small andconsequently the N leaching is almost negligible. It isconcluded that the nitrogen mass balance of this old beechforest ecosystem mainly is controlled by the input by dry andwet deposition and a large internal N cycle with a fast litterturnover. The nitrogen input tothe forest ecosystem which currently exceeds the critical loadby 5 kg N ha^-1 yr ^-1is mainly accumulated in the soil and no significant nitrateleaching is occurring.     

Measuring Eddy Covariance Fluxes of Ammonia Using Tunable Diode Laser Absorption Spectroscopy

Field measurements of NH3 fluxes using an eddy covariance technique were made for a total of 60 days between July and September 2002 at an intensively managed grassland in Southern Scotland. The collected data demonstrate the suitability of a tuneable diode laser absorption spectroscopy (TDLAS) system coupled with a sonic anemometer for eddy covariance measurements. The novelty of these measurements is the application to ammonia, which has only become measurable using TDLAS techniques recently, because of its small ambient concentration. Data presented in this paper show typical features of the fluxes and concentration for the summer season. NH3 concentration and flux values are in a similar range to previous studies using flux gradient methods at the same field site, although the particularly wet season reduced the concentration of NH₃ in the air. For an example day, measured NH₃ fluxes ranged between –11 and 44 ng m^–2 s^–1 with an average value of 3.78 ng m^–2 s^–1 indicating a small net emission from the vegetation. Spectral analysis executed on the data shows the percentage of flux carried by the small eddies (from 0.2 to 2 m) suggesting that high detection frequency instruments are particularly suitable for estimating NH₃ fluxes between atmosphere and vegetation.     

Use of Natural 35S to Trace Sulphate Cycling in Small Lakes,Flattops Wilderness Area,Colorado, U.S.A.

Measurements of the cosmogenically-produced ³⁵S, a radioisotope of sulphur (t_1/2 = 87 days), are reported for the Ned Wilson Lake watershed in Colorado. The watershed contains two small lakes and a flowing spring presumed to be representative of local ground water. The watershed is located in the Flattops Wilderness Area and the waters in the system have low alkalinity, making them sensitive to increases in acid and sulphate deposition. Time series of ³⁵S measurements were made during the summers of 1995 and 1996 (July–September) at all three sites. The system is dominated by melting snow and an initial concentration of 16–20 mBq L^-1 was estimated for snowmelt based on a series of snow samples collected in the Rocky Mountains. The two lakes had large initial ³⁵S concentrations in July, indicating that a large fraction of the lake water and sulphate was introduced by meltwater from that year's snowpack. In 1995 and 1996, ³⁵S concentrations decreased more rapidly than could be accounted for by decay, indicating that other processes were affecting ³⁵S concentrations. The most likely explanation is that exchange with sediments or the biota was removing ³⁵S from the lake and replacing it with older sulphate devoid of ³⁵S. In September of 1995 and 1996, ³⁵S concentrations increased, suggesting that atmospheric deposition is important in the sulphate flux of these lakes in late summer. Sulphur-35 concentrations in the spring water were highly variable but never higher than 3.6 mBq L^-1 and averaged 2 mBq L^-1. Using a simple mixing model, it was estimated that 75% of the spring water was derived from precipitation of previous years.