The Missing Flux in a 35S Budget for the Soils of a Small Polluted Catchment

A combination of cosmogenic and artificial ³⁵S was used to assess the movement of sulfur in a steep Central European catchment affected by spruce die-back. The Jeze?í catchment, Kru?né Hory Mts. (Czech Republic) is characterized by a large disproportion between atmospheric S input and S output via stream discharge, with S output currently exceeding S input three times. A relatively high natural concentration of cosmogenic ³⁵S (42 mBq L^-1) was found in atmospheric deposition into the catchment in winter and spring of 2000. In contrast, stream discharge contained only 2 mBq L^-1. Consequently, more than 95% of the deposited S is cycled or retained within the catchment for more than several months, while older S is exported via surface water. In spring, when the soil temperature is above 0 °C, practically no S from instantaneous rainfall is exported, despite the steepness of the slopes and the relatively short mean residence time of water in the catchment (6.5 months). Sulfur cycling in the soil includes not just adsorption of inorganic sulfate and biological uptake, but also volatilization of S compounds back into the atmosphere. Laboratory incubations of an Orthic Podzol from Jeze?í spiked with 720 kBq of artificial ³⁵S showed a 20% loss of the spike within 18 weeks under summer conditions. Under winter conditions, the ³⁵S loss was insignificant (<5%). This missing S flux was interpreted as volatilized hydrogen sulfide resulting from intermittent dissimilatory bacterial sulfate reduction. The missing S flux is comparable to the estimated uncertainty in many catchment S mass balances (±10%), or even larger, and should be considered in constructing these mass balances. In severely polluted forest catchments, such as Jeze?í, sulfur loss to volatilization may exceed 13 kg ha^-1 a^-1, which is more than the current total atmospheric S input in large parts of North America and Europe.     

Post-Glacial Lead Dynamics in a Forest Soil

The use of alkyl-Pb additives in gasoline during the 20th century resulted in widespread Pb pollution. The objective of this study was to determine the relative importance of atmospherically deposited Pb and Pb released through weathering to soil Pb pools at the Hubbard Brook Experimental Forest, New Hampshire. We employed a selective extraction method to estimate the amount of Pb that was: water-soluble + exchangeable (EX); inorganically bound (IB); organically bound (ORG); bound to amorphous oxides (AMOX); and bound in crystalline minerals (RES). After normalizing crystalline-Pb concentrations to the immobile element Ti, we estimated that 14.1 kg ha^-1 of Pb has been weathered from Hubbard Brook soils in the 12,000–14,000 yr since deglaciation – a long-term average release of 1.0–1.2 g ha^-1 a^-1. Analysis of Ti-normalized total Pb concentrations indicated a net post-glacial decrease of 7.2 kg ha^-1 in the total Pb pool – consisting of a net accumulation of 4.9 kg ha^-1 in the O horizon, and a net loss of 12.1 kg ha^-1 from mineral soil. Atmospheric deposition of Pb between 1926 and 1989 (estimated as 8.7 kg ha^-1) was a major source of Pb in the post-glacial period. Together, long-term weathering release and 20th century atmospheric deposition could account for all of the Pb in the EX, IB, ORG, and AMOX fractions. Lead from gasoline appears to constitute a major fraction of the total Pb burden in Hubbard Brook soils. Periodic analysis of soil Pb fractions may be useful in monitoring the fate of Pb in forest soils.     

Nitrogen Turnover and Nitrate Leaching after Bark Beetle Attack in Mountainous Spruce Stands of the Bavarian Forest National Park

More than 85% of the mountainous spruce forest of the Bavarian Forest National Park died after bark beetle attack during the last decade. The elemental budget of intact stands and of different stages after the dieback was investigated. N-fluxes in throughfall of intact stands were lower (12–16 kg ha^-1 a^-1) than in an earlier study in an intact mountainous spruce stand in the Bavarian Forest National Park and were reduced in the first years after the dieback (3–5 kg N ha^-1 a^-1). Nitrate-N fluxes by seepage water of intact stands at 40 cm depth, which is below the main rooting zone, were moderate (5–9 kg ha^-1 a^-1). After the dieback of the stands, NH₄ ⁺ concentrations were increased in humus efflux as were NO₃ ^- concentrations in mineral soil. Due to the relatively high precipitation, dilution of the elemental concentrations in seepage was considerable.Therefore, NO₃ ^- concentrations were usually below the level of drinking water (806 μmol NO₃ ^- L^-1), with lowest concentrations after the snowmelt and highest in autumn. Nitrate concentrations were elevated from the first year until the 7th year after the dieback. Total NO₃ ^--N losses by seepage until the 7th year after the dieback equalled 543 kg N ha^-1. Aluminium fluxesafter the dieback were enhanced in the mineral soil from 55 to 503 mmol_c m^-2 a^-1 (average of 8 yr), K⁺ fluxes from 8 to 37 mmol_c m^-2 a^-1, and Mg²⁺ fluxes from 13 to 35 mmol_c m^-2 a^-1. The consequences for the nutritional status of the ecosystem, the hydrosphere, and forest management are discussed in the paper.     

Yields of Dissolved Organic C,N, and P. from Three High-Elevation Catchments,Colorado Front Range,U.S.A.

Ecosystem dynamics in high-elevation watersheds are extremely sensitive to changes in chemical, energy, and water fluxes. Here we report information on yields of dissolved organic C, N, and P for the 1999 snowmelt runoff season from three high-elevation catchments in the Colorado Front Range, U.S.A.: Green Lake 4 (GL4) and Albion townsite (ALB) on North Boulder Creek and the Saddle Stream (SS), a tributary catchment dominated by alpine tundra. Dissolved organic carbon (DOC) concentrations in stream waters ranged from <1 to 10 mg C L^-1, with the highest values occurring at the SS site. Dissolved organic nitrogen (DON) concentrations ranged from below detection limits to 0.28 mg N L^-1 and were again highest at the tundra-dominatedsite. Dissolved organic phosphorus (DOP) concentrations were at or near detection limits throughout the season in all three catchments indicating a strong terrestrial retention of P. OnlyDOC showed a significant relationship to discharge. Yields of DOC in the three catchments ranged from 10.6 to 11.8 kg C ha^-1 while yields of DON and DOP ranged from 0.32 to 0.41 and 0.02 to 0.08 kg ha^-1, respectively. The relatively highyield of organic N and P relative to C from the highest elevationsite (GL4) was somewhat surprising and points to either: (1) a source of dissolved organic material (DOM) in the upper reaches of the catchment that is enriched in these nutrients or (2) theselective uptake and processing of organic N and P downstream ofthe sampling site. Additionally, seasonal changes in the relativeimportance of DOM precursor materials appear to result in changesin the N content of DOM at both the GL4 and ALB 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.     

Characterization and phosphate stabilization of dusts from the vitrification of MSW combustion residues

The use of soluble PO₄³⁻ as a heavy metal chemical stabilization agent was evaluated for a dust generated from melting or vitrification of municipal solid waste combustion residues. Vitrification dusts contain high concentrations of volatile elements such as Cl, Na, K, S, Pb, and Zn. These elements are present in the dusts largely as simple salts (e.g. PbCl₂, ZnSO₄) which are highly leachable. At an experimental dose of 0.4 moles of soluble PO₄³⁻ per kg of residue, the pH-dependent leaching (pH 5,7,9) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 100 for many metals; particularly Cd, Cu, Pb and Zn. Bulk and surface spectroscopies showed that the insoluble reaction products are tertiary metal phosphate [e.g. Zn₃(PO₄)₂] and apatite [e.g. Pb₅(PO₄)₃Cl] family minerals. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca²⁺, Zn²⁺, Pb²⁺, Cu²⁺, and Cd²⁺ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids. Soluble phosphate effectively converted soluble metal salts into insoluble metal phosphate phases despite the relatively low doses and dry mixing conditions that were used. Soluble phosphate is an effective stabilization agent for divalent heavy metals in melting dusts where leachable metals are present in high concentrations.     

Assessing Changes in Phosphorus Concentrations in Relation to In-Stream Plant Ecology in Lowland Permeable Catchments: Bringing Ecosystem Functioning Into Water Quality Monitoring

Changes in concentrations of soluble reactive phosphorus (SRP), excess partial pressure of carbon dioxide (EpCO₂), and chlorophyll-a were examined for two rivers in the in the upper Thames catchment: the main river Thames at Wallingford and a chalk stream tributary, the River Kennet. Sampling began in the spring of 1997 and has covered extremes in river flow conditions. During the sampling period there was a dramatic reduction in phosphorus (P) inputs from the introduction of effluent P-treatment at sewage treatment works, as a result of the EU Urban Wastewater Treatment Directive. Despite major reductions in baseflow SRP concentrations in the River Kennet, from around 700 μg-P L^-1 to around 100 μg-P L^-1, observations of aquatic plant communities indicate overall degradation in ecological quality since effluent P-treatment was introduced. The degradation was associated with a spring and summer decline in growth of Ranunculus, a macrophyte of high conservation value in chalk streams, particularly from 2000 onwards, linked to shading by epiphytic algae. Although the EpCO₂ records indicate a reduction in primary productivity since effluent P-treatment, the River Kennet may have become more sensitive to epiphyte blooms. Episodes of epiphyte proliferation appear to be linked temporally to small increases in SRP concentrations (typicallyabove a 100 μg-P L^-1 threshold) under summer baseflow conditions. The in-stream system is highly complex and individual processes and causality are difficult to resolve, particularly given changes in river flows linked to background climatic variability and limited availability of biological data. This study demonstrates the need for integrated long-term biological and chemical monitoring of river systems subject to major perturbations to assess timescales required to produce new dynamic equilibria in ecosystem response.     

Fate and behavior of metal(loid) contaminants in an organic matter-rich shooting range soil: Implications for remediation

This study investigates the fate and behavior of lead (Pb), copper (Cu), antimony (Sb), and arsenic (As) in a shooting range soil. The soil samples were collected from the surface (0–15 cm) and the subsurface (15–40 cm and 40–55 cm) of a grassy and wood chip covered impact area behind a firing position. Optical microscopy images indicate significant amounts of corroded bullet fragments and organic wood chips in the surface soil. Analysis by X-ray powder diffraction (XRPD) and scanning electron microscopy electron dispersive X-ray spectroscopy (SEM-EDS) showed that metallic Pb was transformed into lead oxides (litharge PbO and massicot PbO) and lead carbonates (hydrocerussite Pb₃(CO₃)₂(OH)₂, cerussite PbCO₃, and plumbonacrite Pb₅(CO₃)₃O(OH)₂). Rietveld quantification indicated the surface soil contained 14.1% metallic Pb, 17.9% hydrocerussite, 5.2% plumbonacrite, 5.9% litharge, and 3.9% massicot on a dry weight basis, or a total of 39.7% Pb, far in excess of lead concentrations typically found in US shooting range soils. Metallic Cu (bullet jacket material) appeared stable as no secondary minerals were detected in the surface soil. As and Sb concentrations were on the order of 1,057 mg/kg and 845 mg/kg respectively. The elevated soil pH coupled with high organic carbon content is thought to have caused downward migration of metals, especially for Pb, since 4,153 mg Pb/kg was observed at a depth of 55 cm. More than 60% of Pb was concentrated in the coarse soil (> 0.425 mm) fraction, suggesting soil clean-up possible by physical soil washing may be viable. The concentrations of Pb, As, and Sb in the toxicity characteristic leaching procedure (TCLP) extracts were 8,869 mg/L, 6.72 mg/L, and 6.42 mg/L respectively, were above the USEPA non-hazardous regulatory limit (As and Pb) of 5 mg/L. The elevated Sb and As concentrations draw concern because there is historically limited information concerning these metals at firing ranges and several values exceeded local soil cleanup criteria. As the high Pb concentrations appeared to be linked to the presence of organic-rich berm cover materials, the use of wood chips as berm cover to prevent soil erosion requires reconsideration as a shooting range management practice.     

Dynamics of P, Al, and Fe during High Discharge Episodic Acidification at the Bear Brook Watershed in Maine, U.S.A.

Phosphorus (P), aluminum (Al), and iron (Fe) stream chemistry were assessed for high discharge snowmelt events at the Bear Brook Watershed, Maine (BBWM) during December 2001 and February 2002 and compared with results from a January 1995 study of the same streams. The West Bear catchment has been subjected to artificial acidification since 1989. The East Bear catchment is the untreated reference. Total (acid soluble) Al, Fe, and P were positively correlated with discharge during the 2001–2002 events. However, dissolved P concentrations remained low (≤0.1 μmol L^-1) during high discharge events as pH decreased in both streams.For example, in 2001, total P concentration increased to 1.7 μmol L^-1 during the rising limb of the hydrograph in West Bear, approximately five times the value in East Bear. During the same event, in West Bear and East Bear dissolved Al concentrations increased to 21 and 6.3 μmol L^-1, respectively, while total Al concentrations increased to 166 and 30 μmol L^-1, respectively. Dissolved Fe concentrations remained ≤0.9 μmol L^-1 in both streams during all study events. However, total Fe concentrations in 2001 increased to 239 and 4.1 μmol L^-1 for West Bear and East Bear, respectively. Total Al and Fe declined parallel to total P after peaking during all study periods. Nearly all of the base cations were in dissolved form during the three events, indicating that total Al in West and East Bear Brooks is not associated with primary minerals such as feldspars. We conclude that particulate Al, Fe, and P are chemically linked during transport at high discharge in these episodically and chronically acidified streams.     

A conceptual model of spatially heterogeneous nitrogen leaching from a welsh moorland catchment

Soil- and stream-water data from the Plynlimon research area, mid-Wales, have been used to develop a conceptual model of spatial variations in nitrogen (N) leaching within moorland catchments. Extensive peats, in both hilltop and valley locations, are considered near-complete sinks for inorganic N, but leach the most dissolved organic nitrogen (DON). Peaty mineral soils on hillslopes also retain inorganic N within upper organic horizons, but a proportion percolates into mineral horizons as nitrate (NO^? ₃), either through incomplete immobilisation in the organic layer, or in water bypassing the organic soil matrix via macropores. This NO^? ₃ reaches the stream where mineral soilwaters discharge (via matrix throughflow or pipeflow) directly to the drainage network, or via small N-enriched flush wetlands. NO^? ₃ in hillslope waters discharging into larger valley wetlands will be removed before reaching the stream. A concept of catchment ‘nitrate leaching zones’ is proposed, whereby most stream NO^? ₃ derives from localised areas of mineral soil hillslope draining directly to the stream; the extent of these zones within a catchment may thus determine its overall susceptibility to elevated surface water NO^? ₃ concentrations.     

The Input and Transmission of Fallout Radionuclides Through Redó, a High Mountain Lake in the Spanish Pyrenees

Fallout radionuclides have increasing value as tracers of pathways for pollutant transport through catchment/lake systems, in addition to their more traditional role in dating sediment records. The objectivesof this study, carried out within the EU MOLAR project, were tomeasure atmospheric fluxes of fallout ²¹⁰Pb, ¹³⁷Cs and ⁷Be at Redó, to establish mass balances for theseradionuclides, and test and validate models of pollutant transport through the lake and its catchment. This was achieved by comparing measured fluxes and concentrations in the water column with theoretical estimates using simple compartment models. Several interesting points emerged. Differences betweensoil core and rainwater measurements suggest that Saharan dust may be an important source of fallout ²¹⁰Pb. Fluxes throughthe water column had a clear seasonal trend reflecting winter icecover. Significant concentrations of ¹³⁷Cs are still presentin the water column, due to continued inputs from the catchment and/or remobilisation from the bottom sediments.     

Accumulation of Heavy Metals by in vitro cultures of plants

The aim of the project is to study heavy metals accumulation by the selected plants in both laboratory and field conditions. Within the experiments the aspen (Populus tremula × tremuloides), sunflower (Helianthus annuus) and corn (Zea mays) plants were studied. The reasons for this selection were: a fast growth of these plants, an accumulation capacity and an ability to survive in different types of soils. The study was carried out on the aspen plantlets grown in vitro. The plants were exposed to the aqueous solutions having concentrations 0.1 mM, 0.5 mM of Pb²⁺ or Ni²⁺, respectively. The accumulation capacityfor aspen, was about 70% of Pb²⁺ originally present in the solution. The starting concentration of Pb²⁺ (0.5 mM) exhibited no negative impact on the growth. Besides in vitro expositions, a pilot-scale phytoremediation experiment was carried out at the polluted industrial area (Zn – 75000 mg/kg), (Pb – 16000 mg/kg), (Cr – 590 mg/kg), (Cd – 90 mg/kg) and (Cu – 1700 mg/kg).     

Acidification Trends and the Evolution of Neutralization Mechanisms through Time at the Bear Brook Watershed in Maine (BBWM), U.S.A.

The paired catchment study at the forested Bear Brook Watershed in Maine (BBWM) U.S.A. documents interactions among short- to long-term processes of acidification. In 1987–1989, runoff from the two catchments was nearly identical in quality and quantity. Ammonium sulfate has been added bi-monthly since 1989 to the West Bear catchment at 1800 eq ha^-1 a^-1; the East Bear reference catchment is responding to ambient conditions. Initially, the two catchments had nearly identical chemistry (e.g., Ca²⁺, Mg²⁺, SO₄ ^2-, and alkalinity ≈82, 32, 100, and 5 μeq L^-1, respectively). The manipulated catchment responded initially with increased export of base cations, lower pH and alkalinity, and increased dissolved Al,NO₃ ^- and SO₄ ^2-. Dissolved organic carbon and Si have remained relatively constant. After 7 yr of treatment, the chemical response of runoff switched to declining base cations, with the other analytes continuing their trends; the exports of dissolved and particulate Al, Fe, and P increased substantially as base cations declined. The reference catchment has slowly acidified under ambient conditions, caused by the base cation supply decreasing faster than the decrease of SO₄ ², as pollution abates. Export of Al, Fe and, P is mimicking that of the manipulated watershed, but is lower in magnitude and lags in time. Probable increasing SO₄ ^2- adsorption caused by acidification has moderated the longer-term trends of acidification of both watersheds. The trends of decreasing base cations were interrupted by the effects of several short-term events, including severe ice storm damage to the canopy, unusual snow pack conditions, snow melt and rain storms, and episodic input of marine aerosols. These episodic events alter alkalinity by5 to 15 μeq L^-1 and make it more difficult to determine recovery from pollution abatement.     

A Conceptual Model of Spatially Heterogeneous Nitrogen Leaching from a Welsh Moorland Catchment

Soil- and stream-water data from the Plynlimon research area, mid-Wales, have been used to develop a conceptual model of spatial variations in nitrogen (N) leaching within moorland catchments. Extensive peats, in both hilltop and valley locations, are considered near-complete sinks for inorganic N, but leach the most dissolved organic nitrogen (DON). Peaty mineral soils on hillslopes also retain inorganic N within upper organic horizons, but a proportion percolates into mineral horizons as nitrate (NO ₃ ^– ), either through incomplete immobilisation in the organic layer, or in water bypassing the organic soil matrix via macropores. This NO ₃ ^– reaches the stream where mineral soilwaters discharge (via matrix throughflow or pipeflow) directly to the drainage network, or via small N-enriched flush wetlands. NO ₃ ^– in hillslope waters discharging into larger valley wetlands will be removed before reaching the stream. A concept of catchment nitrate leaching zones is proposed, whereby most stream NO ₃ ^– derives from localised areas of mineral soil hillslope draining directly to the stream; the extent of these zones within a catchment may thus determine its overall susceptibility to elevated surface water NO ₃ ^– concentrations.     

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.     

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.     

Application of tracer ratio and inverse dispersion methods with boat-based plume measurements to estimate ammonia emissions from seabird colonies

Ammonia emissions from two contrasting seabird colonies in Scotland were measured, based on the determination of atmospheric concentrations downwind of the colonies. Atmospheric concentrations of ammonia (NH₃) across the downwind plume were compared with the inverse application of a Gaussian dispersion model (ID) to calculate the modelled NH₃ emission that would generate the measured cross-wind-integrated plume concentration. In parallel, a tracer gas (sulphur hexafluoride, SF₆) was released from the colonies with air samples taken to allow determination of SF₆ concentrations. On the basis of the known emission rate of SF₆, the magnitude of ammonia emissions was estimated by the cross-wind-integrated tracer ratio (TR) of NH₃/SF₆ concentrations. Coupled with data on annual bird attendance, the measurements indicate annual emissions from the Isle of May and the Bass Rock of 18 and 132 tonnes NH₃-N year^?1, respectively. The measured NH₃ emissions were compared with estimates of seabird nitrogen excretion to estimate the proportion of excreted N that is volatilised as NH₃ (F _Nr). The emission estimates of the two methods compared favourably, giving 4 and 6 kg NH₃-N h^?1 (F _Nr = 15%) for the Isle of May for the ID and TR methods, respectively, and 21 and 25 kg NH₃-N h^?1 (F _Nr = 50%) for the Bass Rock for the ID and TR methods, respectively. The results provide the first measurement-based estimates to allow regional up scaling of ammonia emissions from seabirds.     

Application of tracer ratio and inverse dispersion methods with boat-based plume measurements to estimate ammonia emissions from seabird colonies

Ammonia emissions from two contrasting seabird colonies in Scotland were measured, based on the determination of atmospheric concentrations downwind of the colonies. Atmospheric concentrations of ammonia (NH₃) across the downwind plume were compared with the inverse application of a Gaussian dispersion model (ID) to calculate the modelled NH₃ emission that would generate the measured cross-wind-integrated plume concentration. In parallel, a tracer gas (sulphur hexafluoride, SF₆) was released from the colonies with air samples taken to allow determination of SF₆ concentrations. On the basis of the known emission rate of SF₆, the magnitude of ammonia emissions was estimated by the cross-wind-integrated tracer ratio (TR) of NH₃/SF₆ concentrations. Coupled with data on annual bird attendance, the measurements indicate annual emissions from the Isle of May and the Bass Rock of 18 and 132 tonnes NH₃-N year^–1, respectively. The measured NH₃ emissions were compared with estimates of seabird nitrogen excretion to estimate the proportion of excreted N that is volatilised as NH₃ (F_Nr). The emission estimates of the two methods compared favourably, giving 4 and 6 kg NH₃-N h^–1 (F_Nr = 15%) for the Isle of May for the ID and TR methods, respectively, and 21 and 25 kg NH₃-N h^–1 (F_Nr = 50%) for the Bass Rock for the ID and TR methods, respectively. The results provide the first measurement-based estimates to allow regional up scaling of ammonia emissions from seabirds.     

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.     

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.