Modelling atmospheric mercury transport and deposition across Europe and the UK

There are inadequate measurements of surface ambient concentrations of mercury species and their deposition rates for the UK deposition budget to be characterized. In order to estimate the overall mercury flux budget for the UK, a simple long-term 1D Lagrangian trajectory model was constructed that treats emissions (1998), atmospheric transformation and deposition across Europe. The model was used to simulate surface concentrations of mercury and deposition across Europe at a resolution of 50 km×50 km and across the UK at 20 km×20 km. The model appeared to perform adequately when compared with the few available measurements, reproducing mean concentrations of elemental gaseous mercury at particular locations and the magnitude of regional gradients. The model showed that 68% of the UK's mercury emissions are exported and 32% deposited within the UK. Of deposition to the UK, 25% originates from the Northern Hemisphere/global background, 41% from UK sources and 33% from other European countries. The total mercury deposition to the UK is in good agreement with other modelling, 9.9 tonne yr⁻¹ cf. 9.0 tonne yr⁻¹, for 1998. However, the attribution differs greatly from the results of other coarser-scale modelling, which allocates 55% of the deposition to the UK from UK sources, 4% from other European countries and 60% from the global background atmosphere. The model was found to be sensitive to the speciation of emissions and the dry deposition velocity of elemental gaseous mercury. The uncertainties and deficiencies are discussed in terms of model parameterization and input data, and measurement data with which models can be validated. There is an urgent requirement for measurements of removal terms, concentrations, and deposition with which models can be parameterized and validated.     

Modelling the atmospheric fate and seasonality of polycyclic aromatic hydrocarbons in the UK

This paper presents the results from an exercise in atmospheric contaminant fate modelling, which had three main objectives: (1) to investigate the balance between estimated national atmospheric emissions of six selected PAHs and observed ambient measurements for the UK, as a means of testing the current emission estimates; (2) to investigate the potential influence of seasonally dependent environmental fate processes on the observed seasonality of air concentrations; and (3) after undertaking the first two objectives, to make inferences about the likely magnitude of seasonal differences in sources. When addressing objective 1 with annually averaged emissions data, it appeared that the UK PAH atmospheric emissions inventory was reasonably reliable for fluorene, fluoranthene, pyrene, benzo[a]pyrene and benzo[ghi]perylene--but not so for phenanthrene. However, more detailed analysis of the seasonality in environmental processes which may influence ambient levels, showed that the directions and/or magnitudes of the predicted seasonality did not coincide with field observations. This indicates either that our understanding of the environmental fate and behaviour of PAHs is still limited, and/or that there are uncertainties in the emissions inventories. It is suggested that better quantification of PAH sources is needed. For 3- and 4-ringed compounds, this should focus on those sources which increase with temperature, such as volatilisation from soil, water, vegetation and urban surfaces, and possible microbially-mediated formation mechanisms. The study also suggests that the contributions of inefficient, diffusive combustion processes (e.g. domestic coal/wood burning) may be underestimated as a source of the toxicologically significant higher molecular weight species in the winter. It is concluded that many signatory countries to the UNECE POPs protocol (which requires them to reduce national PAH emissions to 1990 levels) will experience difficulties in demonstrating compliance, because source inventories for 1990 and contemporary situations are clearly subject to major uncertainties.     

Cluster analysis applied to atmospheric aerosol samples from the Norwegian Arctic

Cluster analysis is shown to be a useful technique for the identification and characterization of atmospheric aerosol particles. A general procedure for combining the cluster analysis results from a large number of samples is described and shown to be successful for comparing such samples. Two similarity measures, one not previously described, are evaluated for use in cluster analysis.The new analysis procedure was applied to the examination of 11 coarse-fraction and 19 fine-fraction aerosol samples collected during September and October, 1984 at Ny Alesund, Spitzbergen, Norway, ~ 1400 km north of the Arctic Circle. The aerosol at this site consists primarily of Si-, Cl- and S-rich particles, the relative abundance of each varying from sample to sample. Considerable differences in composition were observed between simultaneously collected coarse- and fine-fractions.     

Model simulations of the Arctic atmospheric boundary-layer from the SHEBA year

We present Arctic atmospheric boundary-layer modeling with a regional model COAMPS, for the Surface Heat Budget of the Arctic Ocean (SHEBA) experiment. Model results are compared to soundings, near-surface measurements and forecasts from the ECMWF model. The near-surface temperature is often too high in winter, except in shorter periods when the boundary layer was cloud-capped and well-mixed due to cloud-top cooling. Temperatures are slightly too high also during the summer melt season. Effects are too high boundary-layer moisture and formation of too dense stratocumulus, generating a too deep well-mixed boundary layer with a cold bias at the simulated boundary-layer top. Errors in temperature and therefore moisture are responsible for large errors in heat flux, in particular in solar radiation, by forming these clouds. We conclude that the main problems lie in the surface energy balance and the treatment of the heat conduction through the ice and snow and in how low-level clouds are treated.     

Modelling Tundra Vegetation Response to Recent Arctic Warming

The Arctic land area has warmed by >1 °C in the last 30 years and there is evidence that this has led to increased productivity and stature of tundra vegetation and reduced albedo, effecting a positive (amplifying) feedback to climate warming. We applied an individual-based dynamic vegetation model over the Arctic forced by observed climate and atmospheric CO₂ for 1980–2006. Averaged over the study area, the model simulated increases in primary production and leaf area index, and an increasing representation of shrubs and trees in vegetation. The main underlying mechanism was a warming-driven increase in growing season length, enhancing the production of shrubs and trees to the detriment of shaded ground-level vegetation. The simulated vegetation changes were estimated to correspond to a 1.75 % decline in snow-season albedo. Implications for modelling future climate impacts on Arctic ecosystems and for the incorporation of biogeophysical feedback mechanisms in Arctic system models are discussed.     

Modelling the formation and atmospheric transport of secondary inorganic aerosols with special attention to regions with high ammonia emissions

Regional simulations of sulfate, nitrate and ammonium aerosols were performed by a nested application of the online-coupled three-dimensional Eulerian model system COSMO-MUSCAT. This was done in a domain covering the northern part of Germany and surrounding regions for the full month of May and a 6-week period in August/September 2006 with the primary focus on secondary inorganic aerosol levels caused by ammonia emissions from domesticated animals and agricultural operations.The results show that in situations with westerly winds ammonium nitrate dominates with concentrations of about 5–10 μg m^?3 whereas the ammonium sulfate concentrations are about 5 μg m^?3. In situations with winds mainly from the East characterized by warmer and dryer air the ammonium sulfate concentrations have their maximum at about 10 μg m^?3 whereas at the same time no ammonium nitrate is present.A reduction of agricultural NH₃ emissions by 50% in a regional scale reduces the ammonium nitrate concentrations to a maximum of 30%, while the ammonium sulfate concentrations are unchanged. The reduction of NH₃ emissions in a more limited area (here in the Federal state of Germany Niedersachsen) does have no noticeable effect neither on ammonium sulfate nor on ammonium nitrate.     

Modelling of indoor exposure to nitrogen dioxide in the UK

A dynamic multi-compartment computer model has been developed to describe the physical processes determining indoor pollutant concentrations as a function of outdoor concentrations, indoor emission rates and building characteristics. The model has been parameterised for typical UK homes and workplaces and linked to a time-activity model to calculate exposures for a representative homemaker, schoolchild and office worker, with respect to NO₂. The estimates of population exposures, for selected urban and rural sites, are expressed in terms of annual means and frequency of hours in which air quality standards are exceeded. The annual mean exposures are estimated to fall within the range of 5–21 ppb for homes with no source, and 21–27 ppb for homes with gas cooking, varying across sites and population groups. The contribution of outdoor exposure to annual mean NO₂ exposure varied from 5 to 24%, that of indoor penetration of outdoor air from 17 to 86% and that of gas cooking from 0 to 78%. The frequency of exposure to 1 h mean concentrations above 150 ppb was very low, except for people cooking with gas.     

Long-range transport of some organic compounds to the Norwegian Arctic

Atmospheric emission sources of some chlorinated and polycyclic aromatic hydrocarbons such as fluoranthene are reviewed and their importance for the Arctic is discussed. The origin of these compounds transported to the Arctic is examined using the results of five measurement campaigns in the period of fall 1982-summer 1984 carried out at stations in the Norwegian Arctic. Emissions from sources in the Soviet Union seem to be one of the major contributors to the episodical increased levels of organic pollutants during both wintertime and summertime.     

Modelling the spatial distribution of ammonia emissions from seabirds in the UK

Knowledge of the sources and distribution of ammonia (NH3) emissions underpins our understanding of the nitrogen budget. Research has focused on quantifying NH3 emissions from anthropogenic sources, whilst those from natural sources have received little attention internationally. Seabirds excrete large quantities of nitrogen, making seabird colonies a major natural source of NH3. Ammonia emissions from each UK seabird species were estimated and combined with population distribution data to model their spatial distribution. Total NH3 emissions from UK seabirds were estimated at 2.7 kt per year. Seabird emissions are concentrated in remote parts of the UK where anthropogenic emissions are small, so that seabirds often represent the main source of NH3 emissions in these areas. Seabird NH3 emissions were found to have increased by 34% since the 1970s. This corresponds to population changes which may be influenced by human activities, showing that even this natural source can be anthropogenically modified.     

Deposition of sulfate during stable atmospheric transport over lake michigan

Sulfate concentration measurements were made during very stable atmospheric conditions at-a Lake Michigan sampling site 55 km downwind of Chicago. Chicago sulfate concentrations are compared with the midlake concentrations. Dilution and transformation effects upon downwind sulfate concentrations are considered to be small during the very stable atmospheric conditions encountered. Depositional loss to the lake is then assumed to explain essentially all the differences between Chicago and midlake concentrations. The deposition velocity of sulfate to the lake is found to be 0.2 ± 0.16cms⁻¹ despite the very stable conditions prevailing.     

The stable carbon isotope composition of atmospheric PAHs

A method for compound-specific stable carbon isotope analysis of atmospheric polycyclic aromatic hydrocarbons (PAHs) in carbonaceous aerosols is described. Atmospheric aerosol samples containing PAHs (C-10 to C-20) were collected on filters using a high-volume sampling technique, solvent extracted, taken through a cleanup procedure, separated by gas chromatography, oxidized to CO₂ on-line, and introduced into an isotope ratio mass spectrometer for analysis. The method can be used to determine the isotope composition of a few nanograms of PAHs. This technique was used to analyse and compare the isotope composition of atmospheric PAHs from standards, as well as two samples from urban and rural locations. Isotopic variability in atmospheric PAHs is greater than measurement uncertainties which makes this a potentially useful technique for source identification when used together with concentration measurements.     

Observations of Arctic haze during polar flights from Alaska to Norway

Arctic haze observed during polar flights from Anchorage, Alaska, to Thule, Greenland, and Thule to Bodo, Norway, during March 1983, was widespread over the entire Arctic region flown. The distribution of this haze exhibited strong horizontal and vertical variability resulting from the synopticmeteorological situations encountered: e.g. the presence of fronts and haze transport zones. Condensation nuclei concentrations of about 500 cm⁻³ and aerosol scattering extinction values of about 4 × 10⁻⁵m⁻¹ were typical for Arctic haze layers. Intrusions of stratospheric air into the Arctic troposphere through tropopause folds were observed twice, suggesting that these events might occur quite frequently in the springtime Arctic atmosphere.     

Springtime depletion of tropospheric ozone,gaseous elemental mercury and non-methane hydrocarbons in the European Arctic,and its relation to atmospheric transport

Using a trajectory climatology for the period 1992–2001 we have examined how seasonal changes in transport cause changes in the concentrations of tropospheric ozone (O₃), gaseous elemental mercury (GEM) and non-methane hydrocarbons (NMHCs) observed at the Mt. Zeppelin station, Ny-Ålesund (78.9°N, 11.9°E). During April–June O₃ depletion events were frequently observed in connection with air transport across the Arctic Basin. The O₃ loss was most pronounced in air masses advected close to the surface. This result supports the idea that the O₃ depletion reactions take place in the lowermost part of the atmosphere in the central Arctic Basin. A strong positive correlation between springtime O₃ depletion events and the oxidation of GEM to divalent mercury was found. During air mass advection from Siberia, the Barents Sea and the Norwegian Sea the strongest correlation was observed during April–May, whereas air masses originating from the Canadian Arctic and the central Arctic areas showed the highest O₃–GEM correlation in May–June. We suggest that this 1-month lag could either be due to the position of the marginal ice zone or temperature differences between the northwestern and northeastern air masses. In connection with springtime O₃ depletion events low concentrations of some NMHCs, especially ethane and ethyne, were observed, indicating that both bromine (ethyne oxidant) and chlorine radicals (ethane oxidant) are present in the Arctic atmosphere during spring. In winter, negative correlations between O₃ and NMHCs were found in connection with air transport from Europe and Siberia, which we interpret as O₃ destruction taking place in industrially contaminated plumes.     

Modelling aggregate exposure to pesticides from dietary and crop spray sources in UK residents

Environmental Science and Pollution Research - Human exposure to pesticide mixtures can occur from the diet and other sources. Realistic exposure and risk assessments should include multiple...     

Modelling the atmospheric transport and deposition of sulphur and nitrogen over the United Kingdom and assessment of the influence of SO2 emissions from international shipping

A statistical Lagrangian atmospheric transport model was used to generate annual maps of deposition of sulphur and oxidised and reduced nitrogen for the UK at a 5×5 km² resolution. The model was run using emissions for the year 2002. The model was compared with measurements of gas concentrations (SO₂, NO_x, HNO₃ and NH₃) and of wet deposition and aerosol concentrations of SO₄²⁻, NO₃⁻ and NH₄⁺ from national monitoring networks. Good correlation was obtained, demonstrating that the model is capable of accurately estimating the mass balance and spatial distribution of sulphur and nitrogen compounds in the atmosphere. A future emissions scenario for the year 2020 was used to test the influence of shipping emissions on sulphur deposition in the UK. The results show that, if shipping emissions are assumed to increase at a rate of 2.5% per year, their relative contribution to sulphur deposition is expected to increase from 9% to 28% between 2002 and 2020. The model was compared to both a European scale and a global scale chemical transport model and found to give broad agreement with the magnitude and location of sulphur deposition associated with shipping emissions. Enforcement of the MARPOL convention to reduce the sulphur content in marine fuel to 1% was estimated to result in a 6% reduction in total sulphur deposition to the UK for the year 2020. The percentage area of sensitive habitats with exceedance of critical loads for acidity in the UK was predicted to decrease by 1% with the implementation of the MARPOL convention.     

Toxicity of atmospheric particle-bound PAHs: an environmental perspective

Atmospheric polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants that represent a risk not only to humans, but to all living organisms. High-molecular weight PAHs are more toxic than lighter relatives, and also have a higher tendency to bind onto air particles (i.e., particle matter, PM). PM is a major constituent of air pollution. Adequate assessment of the biological impact of PM requires the analysis, not only of the effects on human health, but also on the environment. Since the aquatic systems work as a natural sink to these air pollutants, assessing the effects of particle-bound PAHs on aquatic organisms may further characterize its potential aquatic toxicity, also providing simple and low-cost alternative assays to investigate PM biological effects in vivo. We review the current scientific literature, addressing the atmospheric PAHs fate, transformation and deposition, pertinent particle-bound PAHs toxicity data, and the potential aquatic toxic burden. Conceptual and experimental procedures that could improve future investigations and risk assessments are also considered.     

Modelling the spatial distribution of ammonia emissions in the UK

Ammonia emissions (NH3) are characterised by a high spatial variability at a local scale. When modelling the spatial distribution of NH3 emissions, it is important to provide robust emission estimates, since the model output is used to assess potential environmental impacts, e.g. exceedance of critical loads. The aim of this study was to provide a new, updated spatial NH3 emission inventory for the UK for the year 2000, based on an improved modelling approach and the use of updated input datasets. The AENEID model distributes NH3 emissions from a range of agricultural activities, such as grazing and housing of livestock, storage and spreading of manures, and fertilizer application, at a 1-km grid resolution over the most suitable landcover types. The results of the emission calculation for the year 2000 are analysed and the methodology is compared with a previous spatial emission inventory for 1996.     

GC-MS analyses and chemometric processing to discriminate the local and long-distance sources of PAHs associated to atmospheric PM2.5

Purpose

This study presents a procedure to differentiate the local and remote sources of particulate-bound polycyclic aromatic hydrocarbons (PAHs).

Methods

Data were collected during an extended PM_2.5 sampling campaign (2009?C2010) carried out for 1?year in Venice-Mestre, Italy, at three stations with different emissive scenarios: urban, industrial, and semirural background. Diagnostic ratios and factor analysis were initially applied to point out the most probable sources. In a second step, the areal distribution of the identified sources was studied by applying the discriminant analysis on factor scores. Third, samples collected in days with similar atmospheric circulation patterns were grouped using a cluster analysis on wind data. Local contributions to PM_2.5 and PAHs were then assessed by interpreting cluster results with chemical data.

Results

Results evidenced that significantly lower levels of PM_2.5 and PAHs were found when faster winds changed air masses, whereas in presence of scarce ventilation, locally emitted pollutants were trapped and concentrations increased. This way, an estimation of pollutant loads due to local sources can be derived from data collected in days with similar wind patterns. Long-range contributions were detected by a cluster analysis on the air mass back-trajectories. Results revealed that PM_2.5 concentrations were relatively high when air masses had passed over the Po Valley. However, external sources do not significantly contribute to the PAHs load.

Conclusions

The proposed procedure can be applied to other environments with minor modifications, and the obtained information can be useful to design local and national air pollution control strategies.