Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.     

Nocturnal boundary layer characteristics and land breeze development in Houston,Texas during TexAQS II

The nocturnal boundary layer in Houston, Texas was studied using a high temporal and vertical resolution tethersonde system on four nights during the Texas Air Quality Study II (TexAQS II) in August and September 2006. The launch site was on the University of Houston campus located approximately 4 km from downtown Houston. Of particular interest was the evolution of the nocturnal surface inversion and the wind flows within the boundary layer. The land–sea breeze oscillation in Houston has important implications for air quality as the cycle can impact ozone concentrations through pollutant advection and recirculation. The results showed that a weakly stable surface inversion averaging in depth between 145 and 200 m AGL formed on each of the experiment nights, typically within 2–3 h after sunset. Tethersonde vertical winds were compared with two other Houston data sets (High Resolution Doppler Lidar and radar wind profiler) from locations near the coastline and good agreement was found, albeit with a temporal lag at the tethersonde site. This comparison revealed development of a land breeze on three nights which began near the coastline and propagated inland both horizontally and vertically with time. The vertical temperature structure was significantly modified on one night at the tethersonde site after the land breeze wind shift, exhibiting near-adiabatic profiles below 100 m AGL.     

Contribution of residential wood combustion to PM10 levels in Portugal

Wood is commonly used in residential combustion for heating purposes; however, it can be a major source of air pollutants, namely fine particles, volatile organic compounds and carbon monoxide. Since 2004, the PM10 daily limit value has been surpassed in Portugal, and the European Commission has stated that plans and programs must be designed in order to reduce these levels. In Portugal, 18% of PM10 emissions are due to residential wood combustion, which may deeply impact the PM10 levels in the atmosphere. The main aim of this study is to investigate the impact of residential wood combustion on the air quality in Portugal. The air quality modelling system MM5/CHIMERE was applied over Portugal for a winter month, for the following three scenarios: the reference scenario, considering the actual emissions of PM10; scenario 1, where residential wood combustion emissions are not considered; and scenario 2, which takes into account a complete conversion from traditional fireplaces to certified appliances (with a 90% reduction in PM emissions). The residential wood combustion contribution to PM10 air quality concentration values during January 2007 ranges from 0 to 14 μg m^?3, with a mean contribution of 10 μg m^?3 in the Lisboa area and 6 μg m^?3 in the Porto region. Concerning the legislated values, the area where the daily average limit value (50 μg m^?3) is exceeded decreases by 46% in the simulation when residential combustion is not considered. The modelling results for scenario 2 are not significantly different from those for scenario 1. In summary, the regulation of the residential wood combustion sector is as an effective way to reduce the PM10 levels in the atmosphere as regards air quality plans and programs.     

Contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs): Application to Southeastern France

A modeling approach has been developed to estimate the contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs). It combines an Eulerian chemical transport model for atmospheric processes (Polair3D/Polyphemus) with a fate and transport model for soil and vegetation (Ourson). These two models were specifically adapted for POPs. Results are presented for benzo(a)pyrene (BaP). As expected no accumulation of BaP in leaf vegetables appears during the growth period for each harvest over the 10 years simulated. For BaP and leaf vegetables, this contamination depends primarily on direct atmospheric deposition without chemical transfer from the soil to the plant. These modeling results are compared to available data.     

Characterisation of particulate exposure during fireworks displays

Little is known about the level and content of exposure to fine particles (PM_2.5) among persons who attend fireworks displays and those who live nearby. An evaluation of the levels of PM_2.5 and their elemental content was carried out during the nine launches of the 2007 Montréal International Fireworks Competition. For each event, a prediction of the location of the firework plume was obtained from the Canadian Meteorological Centre (CMC) of the Meteorological Service of Canada. PM_2.5 was measured continuously with a photometer (Sidepak?, TSI) within the predicted plume location (“predicted sites”), and integrated samples were collected using portable personal samplers. An additional sampler was located on a nearby roof (“fixed site”). The elemental composition of the collected PM_2.5 samples from the “predicted sites” was determined using both a non-destructive energy dispersive ED-XRF method and an ICP-MS method with a near-total microwave-assisted acid digestion. The elemental composition of the “fixed site” samples was determined by the ICP-MS with the near-total digestion method. The highest PM_2.5 levels reached nearly 10 000 μg m^?3, roughly 1000 times background levels. Elements such as K, Cl, Al, Mg and Ti were markedly higher in plume-exposed filters. This study shows that 1) persons in the plume and in close proximity to the launch site may be exposed to extremely high levels of PM_2.5 for the duration of the display and, 2) that the plume contains specific elements for which little is known of their acute cardio-respiratory toxicity.     

Use of Calluna vulgaris to detect signals of nitrogen deposition across an urban–rural gradient

Densely populated cities can experience high concentrations of traffic-derived pollutants, with oxides of nitrogen and ammonia contributing significantly to the overall nitrogen (N) budget of urban ecosystems. This study investigated changes in the biochemistry of in situ Calluna vulgaris plants to detect signals of N deposition across an urban–rural gradient from central London to rural Surrey, UK. Foliar N concentrations and δ¹⁵N signatures were higher, and C/N ratios lower, in urban areas receiving the highest rates of N deposition. Plant phosphorus (P) concentrations were also highest in these areas, suggesting that elevated rates of N deposition are unlikely to result in progressive P-limitation in urban habitats. Free amino acid concentrations were positively related to N deposition for asparagine, glutamine, glycine, phenylalanine, isoleucine, leucine and lysine. Overall, relationships between tissue chemistry and N deposition were similar for oxidised, reduced and total N, although the strength of relationships varied with the different biochemical indicators. The results of this study indicate that current rates of N deposition are having substantial effects on plant biochemistry in urban areas, with likely implications for the biodiversity and functioning of urban ecosystems.     

Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM_2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5–4 km) and between 4 and 27% at the urban scale (4–100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM_2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.     

Discriminating the regional and urban contributions in the North-Western Mediterranean: PM levels and composition

Simultaneous measurements of the PM concentration levels and chemical composition of atmospheric aerosols at a regional background (RB) and an urban background (UB) site, located in the same geographic region, allowed for the determination of their urban and regional contributions. In the specific case of the North-Western region of the Mediterranean the RB amount has been quantified in 18, 13 and 12 μg m^?3 for PM₁₀, PM_2.5 and PM₁, respectively, whereas the UB contribution reached 22, 13 and 8 μg m^?3, respectively. The UB contributions in the Western Mediterranean are much higher than those observed in other European regions; especially concerning the coarse fraction. The high loads of road dust in the urban areas across the Mediterranean may account for these large differences.The urban contributions are extremely enriched in Ca, Fe, Sb, Sn, Cu, Zn, being the main tracers of the road dust, with concentrations up to 6–8 times higher than those at the RB. Elemental carbon and nitrate are mainly derived from direct vehicular emissions. Some industrial tracers (Mn, Pb, Bi) are also enriched in the urban area. The evaluation of the Cu/Sb, Cu/Zn, Cu/Cd and Cu/Pb ratios and the high enrichment of these trace elements versus the Upper Crustal Composition average values corroborates the importance of the road-traffic emissions in the study area, also influencing the RB.The supplementary results from a suburban site in the Balearic Islands and the evaluation of the V/Ni ratios evidence the strong signature of fuel-oil combustion processes, which is a general characteristic of the Mediterranean aerosols.     

Using a reduced Common Representative Intermediates (CRIv2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NO_x active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of ?55 Tg yr^?1 to a net gain of +50 Tg yr^?1.     

Improved land cover and emission factors for modeling biogenic volatile organic compounds emissions from Hong Kong

This paper describes a study of local biogenic volatile organic compounds (BVOC) emissions from the Hong Kong Special Administrative Region (HKSAR). An improved land cover and emission factor database was developed to estimate Hong Kong emissions using MEGAN, a BVOC emission model developed by Guenther et al. (2006). Field surveys of plant species composition and laboratory measurements of emission factors were combined with other data to improve existing land cover and emission factor data. The BVOC emissions from Hong Kong were calculated for 12 consecutive years from 1995 to 2006. For the year 2006, the total annual BVOC emissions were determined to be 12,400 metric tons or 9.82 × 10⁹ g C (BVOC carbon). Isoprene emission accounts for 72%, monoterpene emissions account for 8%, and other VOCs emissions account for the remaining 20%. As expected, seasonal variation results in a higher emission in the summer and a lower emission in the winter, with emission predominantly in day time. A high emission of isoprene occurs for regions, such as Lowest Forest-NT North, dominated by broadleaf trees. The spatial variation of total BVOC is similar to the isoprene spatial variation due to its high contribution. The year to year variability in emissions due to weather was small over the twelve-year period (?1.4%, 2006 to 1995 trendline), but an increasing trend in the annual variation due to an increase in forest land cover can be observed (+7%, 2006 to 1995 trendline). The results of this study demonstrate the importance of accurate land cover inputs for biogenic emission models and indicate that land cover change should be considered for these models.