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.     

Correlating the spatial distribution of atmospheric ammonia with δ15n values at an ammonia release site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using δ¹⁵N values in determining the area of influence around a point NH₃ emission source. δ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the δ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with δ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of δ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of δ¹⁵N enrichment. Significant linear correlations between δ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

The spatial distribution of ammonia emitted from seabirds and its contribution to atmospheric nitrogen deposition in the UK

Simple bioenergetics models were used to derive annual nitrogen excretion rates of each seabird species occurring at colonies in the UK. These were combined with population distribution data and an estimated fraction of nitrogen volatilized to estimate the spatial distribution of NH₃ emissions from seabird colonies at a 1 km resolution. The effect of these emissions on atmospheric NH₃ concentrations and nitrogen deposition in the UK was assessed using the FRAME atmospheric chemistry and transport model. The total emission of NH₃ from the UK seabird colonies is estimated at 2.7 kt yr^?1. Emissions from seabirds are largely concentrated in remote parts of Britain, where agricultural and other anthropogenic emissions are minimal. Although seabirds account for less than 1% of total UK NH₃ emissions (～370 kt yr^?1), their occurrence in remote areas and frequently large colony sizes results in seabirds providing a major fraction of the atmospheric nitrogen deposition for many remote ecosystems.     

The spatial distribution of ammonia emitted from seabirds and its contribution to atmospheric nitrogen deposition in the UK

Simple bioenergetics models were used to derive annual nitrogen excretion rates of each seabird species occurring at colonies in the UK. These were combined with population distribution data and an estimated fraction of nitrogen volatilized to estimate the spatial distribution of NH₃ emissions from seabird colonies at a 1 km resolution. The effect of these emissions on atmospheric NH₃ concentrations and nitrogen deposition in the UK was assessed using the FRAME atmospheric chemistry and transport model. The total emission of NH₃ from the UK seabird colonies is estimated at 2.7 kt yr^–1. Emissions from seabirds are largely concentrated in remote parts of Britain, where agricultural and other anthropogenic emissions are minimal. Although seabirds account for less than 1% of total UK NH₃ emissions (370 kt yr^–1), their occurrence in remote areas and frequently large colony sizes results in seabirds providing a major fraction of the atmospheric nitrogen deposition for many remote ecosystems.     

Chemical characterization of emissions from a municipal solid waste treatment plant

Gaseous emissions are an important problem in municipal solid waste (MSW) treatment plants. The sources points of emissions considered in the present work are: fresh compost, mature compost, landfill leaks and leachate ponds. Hydrogen sulphide, ammonia and volatile organic compounds (VOCs) were analysed in the emissions from these sources. Hydrogen sulphide and ammonia were important contributors to the total emission volume. Landfill leaks are significant source points of emissions of H₂S; the average concentration of H₂S in biogas from the landfill leaks is around 1700 ppmv. The fresh composting site was also an important contributor of H₂S to the total emission volume; its concentration varied between 3.2 and 1.7 ppmv and a decrease with time was observed. The mature composting site showed a reduction of H₂S concentration (<0.1 ppmv). Leachate pond showed a low concentration of H₂S (in order of ppbv). Regarding NH₃, composting sites and landfill leaks are notable source points of emissions (composting sites varied around 30–600 ppmv; biogas from landfill leaks varied from 160 to 640 ppmv).Regarding VOCs, the main compounds were: limonene, p-cymene, pinene, cyclohexane, reaching concentrations around 0.2–4.3 ppmv.H₂S/NH₃, limonene/p-cymene, limonene/cyclohexane ratios can be useful for analysing and identifying the emission sources.     

Long Term NH3 Flux Measurements above Grasslands in The Netherlands

Ammonia concentration gradients were measuredabove a grassland in an agricultural region fromJuly 1998 to July 2000 at the locationSchagerbrug in the Netherlands. They were used tocalculate the surface-atmosphere exchange ofammonia by means of the aerodynamic gradienttechnique. Measurements of the ammonia exchangewere also performed at a grass field that is partof a major wetland reserve in the centre of theNetherlands (Oostvaardersplassen), during theperiod June 1994–September 1995. At Schagerbrug,low net emissions or small depositions weremeasured during the winter months, and a netemission up to 5 kg NH₃ ha^-1 month^-1 in summer. The net annual emission was 26 kgN ha^-1, with manure application contributingabout 50% of this emission. AtOostvaardersplassen mainly deposition occurred,but large emissions were measured in autumn. Themeasured exchange fluxes are compared to modelevaluations that incorporate plant physiologicaldata, such as apoplastic NH₄ ⁺concentrations and pH. Results show a goodagreement between field observations and modelsimulations, although some improvements arenecessary during nighttime periods. Themeasurements are conducted within the GRAMINAEproject, a second tranche project of EC TERI.     

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⁺].     

Influence of aeration on CH4, N2O and NH3 emissions during aerobic composting of a chicken manure and high C/N waste mixture

Co-composting of chicken manure, straw and dry grasses was investigated in a forced aeration system to estimate the effect of aeration rates on NH₃, CH₄ and N₂O emissions and compost quality. Continuous measurements of gas emissions were carried out and detailed gas emission patterns were obtained using an intermittent-aeration of 30 min on/30 min off at rates of 0.01 (A1), 0.1 (A2) and 0.2 (A3) m³ min⁻¹ m⁻³. Concentrations of CH₄ and N₂O at the low aeration rate (A1) were significantly greater than those at the other two rates, but there was no significant difference between the A2 and A3 treatments. CH₄ and N₂O emissions for this mixture could be controlled when the composting process was aerobic and ammonia emissions were reduced at a lower aeration rate. Comparison of CH₄, N₂O, NH₃ emissions and compost quality showed that the aeration rate of the A2 treatment was superior to the other two aeration rates.     

Emissions of ammonia and greenhouse gases during combined pre-composting and vermicomposting of duck manure

Combined pre-composting and vermicomposting has shown potential for reclamation of solid wastes, which is a significant source of ammonia (NH₃), and greenhouse gases (GHG), including nitrous oxide (N₂O), methane (CH₄), and carbon dioxide (CO₂). Earthworms and amendments may both affect physico-chemical characteristics that control gas-producing processes, and thus affect NH₃ and GHG emissions. Here, we used two-way ANOVA to test the effects of addition of reed straw and combined addition of reed straw and zeolite on NH₃ and GHG emissions during pre-composting of duck manure, either with or without a follow-up phase of vermicomposting. Results showed that cumulative N₂O, CH₄, and CO₂ emissions during pre-composting and vermicomposting ranged from 92.8, 5.8, and 260.6 mg kg^?1 DM to 274.2, 30.4, and 314.0 mg kg^?1 DM, respectively. Earthworms and amendments significantly decreased N₂O and CH₄ emissions. Emission of CO₂ was not affected by earthworms, but increased in responses to addition of reed straw. Cumulative NH₃ emission ranged from 3.0 to 8.1 g kg^?1 DM, and was significantly decreased by reed straw and zeolite addition. In conclusion, combined pre-composting and vermicomposting with reed straw and zeolite addition would be strongly recommended in mitigating emissions of N₂O, CH₄, and NH₃ from duck manure. Moreover, this method also provides nutrient-rich products that can be used as a fertilizer.     

Determination of nitrous oxide, methane, and ammonia emissions from a swine waste composting process

The amounts of harmful gas emissions from the process of composting swine waste were determined using an experimental composting apparatus. Forced aeration (19.2–96.1 l/m³/min) was carried out continuously, and exhaust gases were collected and analyzed periodically. With weekly turning and the addition of a bulking agent in order to decrease the moisture content and increase air permeability, the temperature of most of the contents rose to 70°C and composting was complete within 3–5 weeks. NH₃, CH₄, and N₂O emissions were high in the early stage of composting. About 10%–25% of the nitrogen in the raw material was lost as NH₃ gas during composting. The emission rate of NH₃ mainly depended on the aeration rate, so that as the aeration rate rose, the level of NH₃ emissions increased. The CH₄ and N₂O emissions could be kept lower with adequate treatment at more than 40 l/m³/min aeration. N₂O may be mainly the result of the denitrification of NO _x -N in the additional matured compost used as a composting accelerator. Received: September 11, 1998 / Accepted: November 8, 1999     

Incorporation of Seasonal Nitrogen Dynamics within a Long-Term Acidification Model

This paper describes an application of the long termdynamic model, MAGIC, on a monthly timestep, enablingincorporation of the seasonal dynamics associated with abroad understanding of the ecosystem N cycle. The modelhas been applied to the Dargall Lane catchment in theGalloway region of Scotland where marked seasonal Ndynamics are apparent. Mean monthly proportions ofrainfall, runoff, deposition fluxes and net retention ofN are utilised to drive the model on a monthly timestep.Calibration of the model has successfully reproduced thepresent day observed seasonal variation in streamNO₃ and ANC. Prediction of recovery at the siteunder the second sulphur protocol indicates that,although mean annual ANC increases, mean monthly ANC doesnot rise above zero for all months of the year until2010.     

Correlating the Spatial Distribution of Atmospheric Ammonia with δ15N Values at an Ammonia Release Site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using ¹⁵N values in determining the area of influence around a point NH₃ emission source. ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of ¹⁵N enrichment. Significant linear correlations between ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

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.     

A New Diffusion Denuder System for Long-Term,Regional Monitoring of Atmospheric Ammonia and Ammonium

Estimating regional patterns in concentrations of atmosphericammonia (NH₃) gas and ammonium (NH₄ ⁺) in aerosolis essential to assess dry deposition, as well as to test theperformance of long-range transport models. Until now, methods for monitoring NH₃ and NH₄ ⁺ (collectively NH_x) have focused on either passive sampling, which does not sample aerosol NH₄ ⁺, or active sampling techniquessuitable for sampling over several minutes to 24 hr. The classicalactive sampling approach is the diffusion denuder, which typically involves either a complex annular denuder or a long(0.5 m) and fragile glass tube. A new denuder implementationis reported here that has been designed for long-term samplingof NH₃ and NH₄ ⁺. By sampling at just 0.35 L min^-1, the method is suitable for monthly measurementsand uses 0.1 m long glass denuders, which may be sent safelyby the normal postal service to monitoring sites. Two denudersare applied in series to test for adequate NH₃ captureefficiency in each sample, while a subsequent acidified paperfilter collects NH₄ ⁺. The method has been implementedat over 50 sites across the U.K. as part of a new national monitoring network. The detection limit is <0.01 μg m^-3 and the sampling is sufficiently accurate to show theseasonal patterns at different sites. This low-cost method willbe useful to address future trends in NH₃ and NH₄ ⁺, especially in relation to compliance with international agreements to reduce NH₃ emissions.     

SEASONAL AND DIURNAL METHANE EMISSIONS FROM A LANDFILL AND THEIR REGULATION BY METHANE OXIDATION

Rates of methane emission from a Swedish landfill, measured by chamber technique and permanent frames, ranged between 0.034 and 20 mmol CH₄m⁻². h⁻¹on average. The emissions followed a seasonal pattern, with the highest fluxes occurring between September and May. Methane concentrations in soil also followed a seasonal pattern, with a marked decrease during summers. Using the means of methane emission rates from frost-free periods, a stepwise regression model was made, that could explain 95% of the variation. Soil temperature turned out to be the dominating factor, explaining 85% when transformed to a second-degree function. Methane emissions were negatively correlated with soil temperature, which strongly suggests that biological methane oxidation is an important regulating factor. The activity of methane-oxidizing microorganisms was greatest around 0.5–0.6 m depth in the soil profile, and moisture at this level enhanced emissions. The tendency for methane emissions to be higher at night was probably due to the inhibitory influence of low soil temperatures on methane-oxidizing microorganisms.     

Future landfill emissions and the effect of final cover installation--a case study

Municipal solid waste (MSW) landfills are potential long-term sources of emissions. Hence, they need to be managed after closure until they do not pose a threat to humans or the environment. The case study on the Breitenau MSW landfill was performed to evaluate future emission levels for this site and to illustrate the effect of final cover installation with respect to long-term environmental risks. The methodology was based on a comprehensive assessment of the state of the landfill and included analysis of monitoring data, investigations of landfilled waste, and an evaluation of containment systems. A model to estimate future emission levels was established and site-specific predictions of leachate emissions were presented based on scenario analysis. The results are used to evaluate the future pollution potential of the landfill and to compare different aftercare concepts in view of long-term emissions. As some leachable substances became available for water flow during cover construction due to a change in the water flow pattern of the waste, a substantial increase in leachate concentrations could be observed at the site (e.g. concentrations of chloride increased from 200 to 800 mg/l and of ammonia-nitrogen from 140 to about 500 mg/l). A period of intensive flushing before the final cover installation could have reduced the amount of leachable substances within the landfill body and rapidly decreased the leachate concentrations to 11 mg Cl/l and 79 mg NH₄-N/l within 50 years. Contrarily, the minimization of water infiltration is associated with leachate concentrations in a high range for centuries (above 400 mg Cl/l and 200 mg NH₄-N/l) with low concomitant annual emission loads (below 12 kg/year of Cl or 9 kg/year of NH₄-N, respectively). However, an expected gradual decrease of barrier efficiency over time would be associated with higher emission loads of 50 kg of chloride and 30 kg of ammonia-nitrogen at the maximum, but a faster decrease of leachate concentration levels.     

Effect of commercial mineral-based additives on composting and compost quality

The effectiveness of two commercial additives meant to improve the composting process was studied in a laboratory-scale experiment. Improver A (sulphates and oxides of iron, magnesium, manganese, and zinc mixed with clay) and B (mixture of calcium hydroxide, peroxide, and oxide) were added to source-separated biowaste:peat mixture (1:1, v/v) in proportions recommended by the producers. The composting process (T, emissions of CO₂, NH₃, and CH₄) and the quality of the compost (pH, conductivity, C/N ratio, water-soluble NH₄–N and NO₃–N, water- and NaOH-soluble low-weight carboxylic acids, nutrients, heavy metals and phytotoxicity to Lepidium sarivum) were monitored during one year. Compared with the control, the addition of improver B increased pH by two units, led to an earlier elimination of water-soluble ammonia, an increase in nitrates, a 10-fold increase in concentrations of acetic acid, and shortened phytotoxicity period by half; as negative aspect it led to volatilization of ammonia. The addition of improver A led to a longer thermophilic stage by one week and lower concentrations of low-weight carboxylic acids (both water- and NaOH-extractable) with formic and acetic of similar amounts, however, most of the aspects claimed by the improver’s producer were not confirmed in this trial.     

Distributions,Land-source Input and Atmospheric Fluxes of Methane in Jiaozhou Bay

CH₄ concentrations in both the surface and bottom waters of Jiaozhou Bay were determined during four surveys in 2003, which showed variability with both seasons and tidal cycles. Atmospheric fluxes of CH₄ in Jiaozhou Bay showed obvious seasonal and spatial variations, with the highest values occurring in summer and the lowest in winter. The annual emission of CH₄ from Jiaozhou Bay was estimated to be . CH₄ in the water column of Jiaozhou Bay was found to come from several land-sources including riverine water input, sewage water input and groundwater input. The spatial and temporal variation in distributions and atmospheric fluxes of CH₄ in Jiaozhou Bay was influenced mainly by the input of polluted river waters and the sewage effluents along the eastern coast, which highlights the effects of human impacts on CH₄ emission rates.     

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.