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.     

Modeling the surface–atmosphere exchange of ammonia

New parameterizations for surface–atmosphere exchange of ammonia are presented for application in atmospheric transport models and compared with parameterizations of the literature. The new parameterizations are based on a combination of the results of three years of ammonia flux measurements over a grassland canopy (dominated by Lolium perenne and Poa trivialis) near Wageningen, the Netherlands and existing parameterizations from literature. First, a model for the surface–atmosphere exchange of ammonia that includes the concentration at the external leaf surface is derived and validated. Second, a parameterization for the stomatal compensation point (expressed as Γ_s, the ratio of [NH₄⁺]/[H⁺] in the leaf apoplast) that accounts for the observed seasonal variation is derived from the measurements. The new, temperature-dependent Γ_s describes the observed seasonal behavior very well. It is noted, however, that senescence of plants and field management practices will also influence the seasonal variation of Γ_s on a shorter timescale. Finally, a relation that links Γ_s to the atmospheric pollution level of the location through the ‘long-term’ NH₃ concentration in the air is proposed.     

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⁺].     

Ultrafine particle fluxes above four major European cities

Little information is known about the behaviour of ultrafine particles (UFP) on a citywide scale. Total particle number flux, dominated by UFP, and other meteorological parameters were collected from tower sites in Manchester, London, Edinburgh and Gothenburg between 1999 and 2006 using the eddy covariance technique. Averaged diurnal cycles were produced for particle number flux, concentration, sensible heat flux, emission velocity, friction velocity, wind speed and temperature. UFP flux cycles showed clear diurnal trends which were linked to traffic activity and local sources. Wind sector analysis showed contributions to flux from local heavily urbanised areas. A simple parameterised model linking UFP flux to traffic activity, sensible heat and friction velocity above the city was produced.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

European scale application of atmospheric reactive nitrogen measurements in a low-cost approach to infer dry deposition fluxes

A European scale network was established in 2006 as part of the NitroEurope Integrated Project to infer reactive nitrogen (Nr) dry deposition fluxes, based on low-cost sampling of gaseous and aerosol species and inferential modelling. The network provides monthly measurements of NH₃, NH₄⁺, HNO₃ and NO₃⁻, as well as SO₂, SO₄²⁻, HCl, Cl⁻ and base cations at 58 sites. Measurements are made with an established low-cost denuder methodology (DELTA) as a basis to: (1) examine temporal trends and spatial patterns across Europe, (2) improve and calibrate inferential modelling techniques to estimate exchange of Nr species, (3) provide best estimates of atmospheric dry N deposition, and (4) permit an analysis of net GHG exchange in relation to atmospheric and agricultural N inputs at the European scale. Responsibility for measurements is shared among seven European laboratories. An inter-comparison of the DELTA implementation by 6 laboratories at 4 test sites (Montelibretti, Italy; Braunschweig, Germany; Paterna, Spain and Auchencorth, UK) from July to October 2006 provided training for the laboratories and showed that good agreement was achieved in different climatic conditions (87% of laboratory site-means within 20% of the inter-laboratory median). Results obtained from the first year of measurements show substantial spatial variability in atmospheric Nr concentrations, illustrating the major local (NH₃) and regional (HNO₃, NO₃⁻, and NH₄⁺) differences in Nr concentrations. These results provide the basis to develop future estimates of site-based Nr dry deposition fluxes across Europe, and highlight the role of NH₃, largely of agricultural origin, which was the largest single constituent and will dominate dry Nr fluxes at most sites.     

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.     

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.     

Estimating the reduction of urban PM10 concentrations by trees within an environmental information system for planners

Trees have been widely quoted as effective scavengers of both gaseous and particulate pollutants from the atmosphere. Recent work on the deposition of urban aerosols onto woodland allows the effect of tree planting strategies on airborne aerosol concentrations to be quantified and considered within the planning process. By identifying the potential planting locations in the local authority area, and applying them within a dispersion and deposition model, the potential magnitude of reduction in the ambient concentration of PM(10), achievable through urban tree planting, has been quantified for two UK cities. As part of the Environmental Information Systems for Planners (EISP), flow diagrams, based on planning decisions, have incorporated output from the model to make decisions on land use planning ranging from development plans and strategic planning, to development control. In this way, for any new developments that contribute to the local PM(10) level, the mitigation by planting trees can be assessed, and in some cases, reductions can be sufficient to meet air quality objectives for PM(10).     

Measuring Aerosol and Heavy Metal Deposition on Urban Woodland and Grass Using Inventories of 210Pb and Metal Concentrations in Soil

The deposition of aerosols to trees has proved very difficult to quantify, especially in complex landscapes. However, trees are widely quoted to be efficient scavengers of particles from the atmosphere, and a growing proportion of the pollutant burden in the atmosphere is present in the aerosol phase. In this study, the deposition of aerosols onto woodland and grass was quantified at a range of locations throughout the West Midlands of England. The sites included mature deciduous woodland in Edgbaston, and Moseley, and mixed woodland at sites within Sutton Park, a large area of semi-natural vegetation. Aerosol deposition to areas of grassland close to the woodland at each site was also measured. Detailed inventories of ²¹⁰Pb in soils within the woodland and in grassland soils, together with concentrations in the atmosphere and precipitation, provided the necessary data to calculate the long-term (about 40 years) annual deposition of sub-micron aerosols onto grassland and woodland. The soil inventories of ²¹⁰Pb under woodland exceeded those under grass, by between 22% and 60%, with dry deposition contributing 24% of the total input flux for grass and 47% for woodland. The aerosol dry deposition velocity to grassland averaged 3.3 mm s^-1 and 9 mm s^-1 for woodland. The large deposition rates of aerosols onto woodland relative to grass or other short vegetation (× 3), and accumulation of heavy metals within the surface horizons of organic soils, leads to large concentrations in soils of urban woodland. Concentrations in the top 10 cm of these woodland soils averaged 252 mg kg^-1 for Pb with peaks to 400 mg kg^-1. Concentrations of Cd averaged 1.4 mg kg^-1, Cu, 126 mg kg^-1, Ni 23 mg kg^-1 and Zn 173 mg kg^-1. The accumulated Pb in urban woodland soils is shown to be large relative to UK emissions.