Modeling effects of traffic and landscape characteristics on ambient nitrogen dioxide levels in Connecticut

An integrated exposure model was developed that estimates nitrogen dioxide (NO(2)) concentration at residences using geographic information systems (GIS) and variables derived within residential buffers representing traffic volume and landscape characteristics including land use, population density and elevation. Multiple measurements of NO(2) taken outside of 985 residences in Connecticut were used to develop the model. A second set of 120 outdoor NO(2) measurements as well as cross-validation were used to validate the model. The model suggests that approximately 67% of the variation in NO(2) levels can be explained by: traffic and land use primarily within 2 km of a residence; population density; elevation; and time of year. Potential benefits of this model for health effects research include improved spatial estimations of traffic-related pollutant exposure and reduced need for extensive pollutant measurements. The model, which could be calibrated and applied in areas other than Connecticut, has importance as a tool for exposure estimation in epidemiological studies of traffic-related air pollution.     

Will photosynthetic capacity of aspen trees acclimate after long-term exposure to elevated CO2 and O3?

Photosynthetic acclimation under elevated carbon dioxide (CO₂) and/or ozone (O₃) has been the topic of discussion in many papers recently. We examined whether or not aspen plants grown under elevated CO₂ and/or O₃ will acclimate after 11 years of exposure at the Aspen Face site in Rhinelander, WI, USA. We studied diurnal patterns of instantaneous photosynthetic measurements as well as A/C_i measurements monthly during the 2004-2008 growing seasons. Our results suggest that the responses of two aspen clones differing in O₃ sensitivity showed no evidence of photosynthetic and stomatal acclimation under either elevated CO₂, O₃ or CO₂ + O₃. Both clones 42E and 271 did not show photosynthetic nor stomatal acclimation under elevated CO₂ and O₃ after a decade of exposure. We found that the degree of increase or decrease in the photosynthesis and stomatal conductance varied significantly from day to day and from one season to another.     

Chemical fluxes in time through forest ecosystems in the UK - Soil response to pollution recovery

Long term trend analysis of bulk precipitation, throughfall and soil solution elemental fluxes from 12 years monitoring at 10 ICP Level II forest sites in the UK reveal coherent national chemical trends indicating recovery from sulphur deposition and acidification. Soil solution pH increased and sulphate and aluminium decreased at most sites. Trends in nitrogen were variable and dependant on its form. Dissolved organic nitrogen increased in bulk precipitation, throughfall and soil solution at most sites. Nitrate in soil solution declined at sites receiving high nitrogen deposition. Increase in soil dissolved organic carbon was detected - a response to pollution recovery, changes in soil temperature and/or increased microbial activity. An increase of sodium and chloride was evident - a possible result of more frequent storm events at exposed sites. The intensive and integrated nature of monitoring enables the relationships between climate/pollutant exposure and chemical/biological response in forestry to be explored.     

Global scale emission and distribution of sea-spray aerosol: Sea-salt and organic enrichment

The chemical composition of marine aerosols as a function of their size is an important parameter for the evaluation of their impact on the global climate system. In this work we model fine particle organic matter emitted by sea spray processes and its influence on the aerosol chemical properties at the global scale using the off-line global Chemistry-Transport Model TM5. TM5 is coupled to a microphysical aerosol dynamics model providing size resolved information on particle masses and numbers. The mass of the emitted sea spray particles is partitioned between water insoluble organic matter (WIOM) and sea salt components in the accumulation mode using a function that relates the emitted organic fraction to the surface ocean chlorophyll-a concentrations. The global emission in the sub-micron size range of organic matter by sea spray process is 8.2 Tg yr^?1, compared to 24 Tg fine yr^?1 sea-salt emissions. When the marine sources are included, the concentrations of modelled primary particulate organic matter (POM) increase mainly over the oceans. The model predictions of WIOM and sea salt are evaluated against measurements carried out at Mace Head (Northern Hemisphere) and Amsterdam Island (Southern Hemisphere), showing that in clean marine conditions WIOM marine emissions contribute significantly to POM values.     

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.     

Humic acid in ice: Photo-enhanced conversion of nitrogen dioxide into nitrous acid

Laboratory studies on the heterogeneous conversion of nitrogen dioxide into nitrous acid on irradiated ice films containing humic acid are described. It was found that the presence of light in the visible range of the solar spectrum significantly enhances the rate of nitrous acid release from a humic acid doped ice film. This process might contribute to observed HONO production in snow, where the NO₂ is thought to originate from nitrate photolysis. Analysis of the experimental data based on the Langmuir Hinshelwood model framework allowed quantification of the observed dependencies of the nitrous acid production rate on nitrogen dioxide concentration. The observed dependencies on the humic acid concentration as well as on the irradiation intensity were used to estimate light-driven HONO fluxes for environmental snow covers.     

Quantifying trace gas emissions from composite landscapes: A mass-budget approach with aircraft measurements

Quantifying trace gas emissions and the influence of surface exchange processes on the atmosphere is a necessary step towards the control of global greenhouse gas emissions and reliability of air quality models. This paper proposes a procedure based on the mass balance method and implemented on highly resolved aircraft data. It allows one to estimate surface exchanges on areas of several km² and heterogeneous features exploiting the characteristics of convective boundary layer during steady state conditions that permit the estimation of emission/absorption terms as functions of advective fluxes only. A nonparametric approach is adopted and the fluxes on the surface of a virtual box surrounding the area of interest are reconstructed on the basis of scalar densities and wind vectors using Shepard functions. Two different techniques are also proposed to face lack of data on the top surface of the box. The method has been applied to experimental data coming from measurement campaigns on two different sites. It provides realistic estimates of the CO₂ emission/absorption in the considered areas that are in good agreement with CO₂ fluxes evaluated by Airborne Eddy Covariance and confirm the suitability of the proposed approach for the assessment of turbulent exchange of trace gases by composite landscapes. Uncertainties on the estimated emissions due to both propagation of the experimental error and interpolation have been quantified by bootstrap analysis as 6%.     

Sea salt concentrations across the European continent

The oceans are a major source for particles that play an important role in many atmospheric processes. In Europe sea salt may contribute significantly to particulate matter concentrations. We have compiled sodium concentration data as a tracer for sea salt for 89 sites in Europe to provide more insight in the distribution of sea salt across Europe. The annual average sea salt concentrations above land were estimated to range between 0.3 and almost 13 μg m^?3. Maximum concentrations are found at the Irish coast. At coastal sites along the Atlantic and North Sea coast concentrations tend to be around 5 μg m^?3. More inland locations up to about 300 km away from the coast tend to show concentrations between 2 and 5 μg m^?3, whereas sites further away from the coast are characterized by lower concentrations. An analysis of the representativity of the data with respect to a long term average showed that the long average is associated with a standard deviation of around 15%. The compilation of observations provides an improved overview of sea salt concentrations in Europe as well as an improved basis for model validation. Verification of the results of the LOTOS-EUROS model learned that the model represents well the spatial variability of the observed sea salt concentrations very well. However, the absolute concentrations are significantly overestimated due to large uncertainties in the emission and dry deposition parameterizations. Using the high explained variability in the gradients across Europe, the bias-corrected modelled distribution serves as a best estimate of the sea salt distribution across Europe for 2005.     

Urban tracer dispersion experiments during the second DAPPLE field campaign in London 2004

As part of the DAPPLE programme two large scale urban tracer experiments using multiple simultaneous releases of cyclic perfluoroalkanes from fixed location point sources was performed. The receptor concentrations along with relevant meteorological parameters measured are compared with a three screening dispersion models in order to best predict the decay of pollution sources with respect to distance. It is shown here that the simple dispersion models tested here can provide a reasonable upper bound estimate of the maximum concentrations measured with an empirical model derived from field observations and wind tunnel studies providing the best estimate. An indoor receptor was also used to assess indoor concentrations and their pertinence to commonly used evacuation procedures.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.