Detecting the signal of atmospheric N deposition in recent national-scale vegetation change across Britain

Model estimates of NO_y and NH_x deposition across Britain for 1996 (5 km square resolution) were applied as explanatory variables to account for national-scale, fine-grained changes in plant species composition between 1990 and 1998. Plant species data were recorded from up to 27 fixed plots located within a stratified random sample of 596 1 km². The response variable was a cover-weighted Ellenberg fertility score for each plot. Analyses were carried out separately for woodlands, semi-natural grasslands and heaths/bogs. Most of the variation in the botanical response variable occurred between plots within squares and so could not be explained by the model deposition data. NH_x deposition estimates accounted for significant, but small components of between 1 km² variation in the change in Ellenberg score in grasslands (5.6%) and heath/bogs (9.8%) but not woodlands. NO_y deposition estimates were not significantly associated with vegetation change. Linear models provided the best fit and the slope of the relationship was lower for heath/bogs than grasslands. Further signal attribution at sub-kilometre square scales requires the development of fine-grained models of N deposition that can be generalised across regional sampling domains.     

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⁺ ₄and 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.     

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 worl” treatment patterns (no rain=no treatment). Simulated precipitation is supplied at ionic concentrations below 4 mM in 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.     

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.     

Early effects of atmospheric ammonia deposition on Calluna vulgaris (L.) hull growing on an ombrotrophic peat bog

This paper reports data from a field study investigating the impacts of elevated ammonia (NH₃) deposition on Calluna vulgaris growing on an ombrotrophic peat bog in S.E. Scotland. Shoot extension, foliar N concentrations, chlorophyll concentration and chlorophyll fluorescence were measured during the second growing season of exposure to a gradient of ammonia concentrations. Results indicate that NH₃ increases growth between 150–200 kg N ha^?1y^?1 cumulative deposition. Foliar N content increased significantly in response to NH₃ cumulative deposition up to 400 kg N ha^?1 y^?1 whereas chlorophyll a content significantly decreased. Measurements of Fv/Fm suggest that although NH₃ exposure altered the growth and reduced chlorophyll a, the efficiency of photosystem II was insensitive to NH₃–N deposition at this stage.     

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.     

Early Effects of Atmospheric Ammonia Deposition on Calluna Vulgaris (L.) Hull Growing on an Ombrotrophic Peat Bog

This paper reports data from a field study investigating the impacts of elevated ammonia (NH₃) deposition on Calluna vulgaris growing on an ombrotrophic peat bog in S.E. Scotland. Shoot extension, foliar N concentrations, chlorophyll concentration and chlorophyll fluorescence were measured during the second growing season of exposure to a gradient of ammonia concentrations. Results indicate that NH₃ increases growth between 150–200 kg N ha^–1y^–1 cumulative deposition. Foliar N content increased significantly in response to NH₃ cumulative deposition up to 400 kg N ha^–1 y^–1 whereas chlorophyll a content significantly decreased. Measurements of Fv/Fm suggest that although NH₃ exposure altered the growth and reduced chlorophyll a, the efficiency of photosystem II was insensitive to NH₃-N deposition at this stage.     

Effects of Nitrogen Deposition on Bryophyte Species Composition of Calcareous Grasslands

Regular additions of NH₄NO₃ (35–140 kg N ha⁻¹ yr⁻¹) and (NH₄)₂SO₄ (140 kg N ha⁻¹ yr⁻¹) to a calcareous grassland in northern England over a period of 12 years have resulted in a decline in the frequency of the indigenous bryophyte species and the establishment of non-indigenous calcifuge species, with implications for the structure and composition of this calcareous bryophyte community. The lowest NH₄NO₃ additions of 35 kg N ha⁻¹ yr⁻¹ produced significant declines in frequency of Hypnum cupressiforme, Campylium chrysophyllum, and Calliergon cuspidatum. Significant reductions in frequency at higher NH₄NO₃ application rates were recorded for Pseudoscleropodium purum, Ctenidum molluscum, and Dicranum scoparium. The highest NH₄NO₃ and (NH₄)₂SO₄ additions provided conditions conducive for the establishment of two typical calcifuges – Polytrichum spp. and Campylopus introflexus, respectively. Substrate-surface pH measurements showed a dose-related reduction in pH with increasing NH₄NO₃ deposition rates of 1.6 pH units between the control and highest deposition rate, and a further significant fall in pH, of >1 pH unit, between the NH₄NO₃ and (NH₄)₂SO₄ treatments. These results suggest that indigenous bryophyte composition may be at risk from nitrogen deposition rates of 35 kg N ha⁻¹ yr⁻¹ or less. These effects are of particular concern for rare or endangered species of low frequency.     

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.     

High Immobilization of NH4+ in Danish Heath Soil Related to Succession,Soil and Nutrients: Implications for Critical Loads of N

During recent decades heathlands havechanged into grasslands in regions with high atmosphericnitrogen deposition. In regions with intermediatedeposition level (e.g., Denmark) changes have been lesspronounced which may be due to delay or decrease inresponse of the ecosystem. The mor layer (O horizon) mayplay an important role for this delay due to high sinkstrength for N. In this study, the capacity for netNH₄ ⁺ immobilization and mineralization wasstudied during short- and long-term incubations (2–36 days)of mor samples from Danish dry inland heaths. High short-term capacity for net NH₄ ⁺ immobilization wasfound to be a general characteristic of Danish heath morlayers both under heather (Calluna vulgaris) andcrowberry (Empetrum nigrum ssp nigrum), the latterdominating late stages in heathland succession. The netNH₄ ⁺ immobilization was higher under youngcompared to old or dead vegetation, and higher on lessnutrient poor soils than on extremely nutrient poor soils.The addition of N, P and C stimulated CO₂ productionand net NH₄ ⁺ immobilization, but not net Nmineralization. The immobilization of ¹⁵NH₄ ⁺caused release of dissolved organic N, increased N anddecreased C/N ratio in the microbial biomass, and indicatedgrowth of microorganisms with other metabolic abilitiesthan the indigenous population. No evidence was obtained ofstabilization of immobilized ¹⁵NH₄ ⁺ intosoil organic matter during the experiment. On background ofthe results and current knowledge it was concluded that therecognition of the high capacity for net NH₄ ⁺immobilization in mor layers does not allow for a raiseof critical loads for N for northern dry inland heaths.     

Integrated Nitrogen and Flow Modelling (INCA) in a Boreal River Basin Dominated by Forestry: Scenarios of Environmental Change

A new version (v1.7) of the Integrated Nitrogen in CAtchments model(INCA) was applied to the northern boreal Simojoki river basin (3160 km²) in Finland. The INCA model is a semi-distributed, dynamic nitrogen (N) process model which simulates N transport and processes in catchments. The INCA model was applied to model flow and seasonal inorganic N dynamics of the river Simojoki basin over the period 1994–1996, and validated for two more years. Both calibration and validation of the model were successful. The model was able to simulate annual dynamics of inorganic N concentrations in the river. The effects of forest management and atmospheric deposition on inorganic N fluxes to the sea in 2010 were studied. Three scenarios were applied for forestry practices and two for deposition. The effects of forest cutting scenarios and atmospheric deposition scenarios on inorganic N flux to the sea were small. The combination of the maximum technically possible reduction of N deposition and a decrease of 100% in forest cutting and peat mining areas decreased NO₃ ^--N flux by 6.0% and NH₄ ⁺-N flux by 3.1%.     

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.     

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.     

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.     

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.     

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     

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.     

Characteristics of NO2 Pollution in the City of Gothenburg, South-West Sweden—Relation to NO x and O3 Levels, Photochemistry and Monitoring Location

Concentrations of NO₂, NO, and O₃ from a rooftop monitoring station in Gothenburg, Sweden (2002–2006) were analysed to characterise NO₂ pollution. [NO₂] was shown to correlate strongly and non-linearly with [NO _x ] (NO _x ?=?NO?+?NO₂), in line with observations in other cities. The [NO₂] to [NO _x ] fraction fell initially with increasing [NO _x ]. At [NO _x ] levels >200 ppb, the decline in [NO₂]/[NO _x ] with increasing [NO _x ] levelled out and [NO₂]/[NO _x ] converged towards approximately 0.15–0.16, independent of [NO _x ]. Data from a traffic route site showed the same pattern. This value of [NO₂]/[NO _x ] at high [NO _x ] can be interpreted as the NO₂ fraction of the NO _x emissions from vehicle exhaust. Situations with high NO _x pollution and minimum [NO₂]/[NO _x ] were always associated with [O₃] close to zero. Plotting [Ox] (Ox?=?NO₂?+?O₃) vs. [NO _x ] provided a strong linear correlation for situations dominated by local pollution ([NO]/[NO₂]>1). The slope of the regression, a measure of the primary NO₂ fraction in NO _x emissions, was 0.13 during the day and 0.14 during the night. With stronger winds, the rooftop monitoring station became more similar, in terms of NO₂ pollution, to a city street site and a traffic route site, although [NO₂] was almost always higher at the street/traffic route locations. The EU standard for the annual average of [NO₂] (40 μg m^?3) was exceeded, while the hourly standard (200 μg m^?3, not to be exceeded more than 18 times per year by 2010) was not exceeded at any of the sites.     

Nitrate Leaching From a Mountain Forest Ecosystem with Gleysols Subjected to Experimentally Increased N Deposition

Nitrate leaching was measured over seven years of nitrogen (N) addition in a paired-catchment experiment in Alptal, central Switzerland (altitude: 1200 m, bulk N deposition: 12 kg ha^-1 a^-1). Two forested catchments (1500 m² each) dominated by Picea abies) were delimited by trenches in the Gleysols. NH₄NO₃ was added to one of the catchments using sprinklers. During the first year, the N addition was labelled with ¹⁵N. Additionally, soil N transformationswere studied in replicated plots. Pre-treatment NO₃ ^--N leaching was 4 kg ha^-1 a^-1 from both catchments, and remained between 2.5 and 4.8 kg ha^-1 a^-1 in the control catchment. The first year of treatment induced an additional leaching of 3.1 kg ha^-1, almost 90% of which was labelled with ¹⁵N, indicating that it did not cycle through the large N pools of the ecosystem (soil organic matter and plants). These losses partly correspond to NO₃ ^- from precipitation bypassing the soil due to preferential flow. During rain or snowmelt events, NO₃ ^- concentration peaks as the water table is rising, indicating flushing from the soil. Nitrification occurs temporarily along the water flow paths in the soil and can be the source of NO₃ ^- flushing. Its isotopic signature however, shows that this release mainly affects recently applied N, stored only between runoff events or up to a few weeks. At first, the ecosystem retained 90% of the added N (2/3 in the soil), but NO₃ ^- losses increased from 10 to 30% within 7 yr, indicating that the ecosystem became progressively N saturated.     

Study of Bulk and Sub-Event Wet Deposition in Gebze,Turkey

This study presents the chemical composition of bulk deposition during the period of February 1996–May 1997 and the chemical composition of sub-event wet deposition on 13 August 1997 in Gebze. Samples were analyzed for SO₄ ^2-, NO₃ ^-, Cl^-,Ca²⁺, Mg²⁺, K⁺, Na⁺, and NH₄ ⁺ in addition to pH. The source of some ionic components in the bulk deposition such as K⁺ and Ca²⁺ were found to be the terrestrial regions, as expected. The (non-sea Cl^-)/Cl^- ratio of 0.05 suggests that the very large portion of Cl^- in the bulkdeposition was of marine origin. The ratio of (non-sea SO₄ ^2-)/SO₄ ^2- varied between 0.86 and 0.99,indicating that the main source of sulfate was not the sea. It is found that the sulfate and calcium concentrations were highest in summer and lowest in fall. The analysis of bulk deposition also indicated that nearly 24% of the events were acidic (pH < 5.6). During sub-event wet deposition collectedon the same site pH decreased continually, and during the passageof cold front concentrations of Cl^-, SO₄ ^2- and NO₃ ^- increased.