Atmospheric Environment (v.41, #40)

An emission inventory for persistent organic pollutants (POP) is made for the year 2000 based on submissions of emission data from the Parties to the Convention on LRTAP. The inventory covers the UNECE territory except Canada and the United States. For the countries, sources or compounds lacking in official submissions, default emission estimates have been prepared and applied to complete the inventory. An indicative comparison of the year 2000 emissions with the 1990 emission levels from a previous study is presented as well as emission projections for 2010, 2015, 2020 based on activity scenarios developed in the framework of the EU CAFE programme. The key source analysis of the projected emissions assuming full implementation of the UNECE protocols allows identification of remaining source strengths which subsequently are briefly discussed in terms of their potential for (further) reduction. A number of chemicals are currently being investigated for inclusion on the UN/ECE POPs protocol list of priority compounds but for these substances emission estimation methodologies are scarce or non-existent. For eight of these substances (dicofol, edosulfan, hexachlorobutadiene (HBU), pentabromodiphenyl ether (PBDE), pentachlorobenzene (PCBe), pentachlorophenol (PCP), polychloronated naftalenes (PCN) and short chained chlorinated paraffins (SCCPs)) an emission estimation methodology is proposed and a preliminary emission inventory for the year 2000 is presented.
Keywords: Emission inventory; HCB; HCH; PCB; PCDD/F; PAH indicator compounds; Europe; Candidate POPs; Emission projection;

Extensive research for establishing the emissions of heavy metals from coal-fired power stations is performed in the Netherlands for the past 25 years. In the Netherlands coal is fired from all over the world. This means that the emissions are established for coal of various origins. In the eighties, the emissions of installations equipped with ESPs (electrostatic precipitators) were measured. In the nineties, the influence of wet FGD (flue gas desulphurisation) on the emissions was studied. The effect of co-combustion of biomass and other secondary fuels is the main item for the last 10 years.Fifty-five elements were measured in the solid state and eight elements in the gaseous phase. It appeared that at low particulate concentration the influence of calcium containing evaporated water droplets downstream the wet FGD on the emissions of heavy metals is bigger than the composition of the coal. Also it appeared that at modern coal-fired power stations the emissions are hardly influenced by co-combustion of biomass. All the results are used for modelling, resulting in the KEMA TRACE MODEL®, by which the emissions can be predicted. The established emission factors are for most elements in good agreement with literature values for comparable modern installations.Persistence organic pollutants (POPs) that were detected in the flue gases of coal-fired power stations are polycyclic aromatic hydrocarbons (PAH) and dioxins/furans. Measurements during full coal-firing and during co-firing of biomass have indicated that these emissions are negligible.
Keywords: Emission factors; Coal-fired power stations; Co-firing; Heavy metals; PAH; Dioxins;

Transport of nitrogen oxides, carbon monoxide and ozone to the Alpine Global Atmosphere Watch stations Jungfraujoch (Switzerland), Zugspitze and Hohenpeissenberg (Germany), Sonnblick (Austria) and Mt. Krvavec (Slovenia) by August Kaiser; Helfried Scheifinger; Wolfgang Spangl; Andrea Weiss; Stefan Gilge; Wolfgang Fricke; Ludwig Ries; Danijel Cemas; Brigita Jesenovec (9273-9287).
The Alpine stations Zugspitze, Hohenpeissenberg, Sonnblick, Jungfraujoch and Mt. Krvavec contribute to the Global Atmosphere Watch Programme (GAW) of the World Meteorological Organization (WMO). The aim of GAW is the surveillance of the large-scale chemical composition of the atmosphere. Thus, the detection of air pollutant transport from regional sources is of particular interest. In this paper, the origin of NO x (measured with a photo-converter), CO and O3 at the four Alpine GAW stations is studied by trajectory residence time statistics. Although these methods originated during the early 1980s, no comprehensive study of different atmospheric trace gases measured simultaneously at several background observatories in the Alps was conducted up to present.The main NO x source regions detected by the trajectory statistics are the northwest of Europe and the region covering East Germany, Czech Republic and southeast Poland, whereas the main CO source areas are the central, north eastern and eastern parts of Europe with some gradient from low to high latitudes. Subsiding air masses from west and southwest are relatively poor in NO x and CO.The statistics for ozone show strong seasonal effects. Near ground air masses are poor in ozone in winter but rich in ozone in summer. The main source for high ozone concentration in winter is air masses that subside from higher elevations, often enhanced by foehn effects at Hohenpeissenberg. During summer, the Mediterranean constitutes an important additional source for high ozone concentrations.Especially during winter, large differences between Hohenpeissenberg and the higher elevated stations are found. Hohenpeissenberg is frequently within the inversion, whereas the higher elevated stations are above the inversion.Jungfraujoch is the only station where the statistics detect an influence of air rich in CO and NO x from the Po Basin.
Keywords: Air pollutant transport; Trajectory residence time statistics;

Dust storm frequency and its relation to climate changes in Northern China during the past 1000 years by Bao Yang; Achim Bräuning; Ziyin Zhang; Zhibao Dong; Jan Esper (9288-9299).
Dust storm events and their relation to climate changes in Northern China during the past 1000 years were analyzed by using different paleoclimate archives such as ice cores, tree rings, and historical documents. The results show that in the semiarid region, the temperature and precipitation series were significantly negatively correlated to the dust storm frequency on a decadal timescale. Compared with temperature changes, however, there was a closer correlation between precipitation changes and dust storm events on a centennial timescale. At this timescale, precipitation accounts for 40% of the variance of dust fall variations during the last 1700 years, inferring precipitation control on the formation of dust storms. In the western arid region, both temperature and precipitation changes are important forcing factors for the occurrence of dust storms in the region on a centennial timescale. In the eastern arid region, the relationship between dust storm events and climate changes are similar like in the semiarid region. As a result, the effects of climate change on dust storm events were manifested on decadal and centennial timescales during the last millennium. However, there is a phase shift in the relation between climate change and the dust storm frequency. A 1400 years reconstruction of the strength of the Siberian High reveals that long-term variations of spring Siberian High intensity might provide a background for the dynamic conditions for the frequency of historical dust storm events in Northern China.
Keywords: Climate change; Dust storm; Northern China; Past 1000 years;

Structural insulated panels (SIPs) have significant environmental and energy advantages. However, the tight structure that results may cause degraded indoor air quality and the potential release of volatile organic compounds (VOCs) from these layered materials must be considered. A physically based model for predicting VOC emissions from multi-layer materials is described. Fugacity is used to eliminate the concentration discontinuities at the interface between layers. This avoids an obstacle associated with numerically simulating mass transfer in composite materials. The numerical model is verified for a double-layer system by comparing predicted concentrations to those obtained with a previously published analytical model. In addition, hexanal emissions from multi-layer SIPs are simulated to demonstrate the usefulness of the fugacity approach. Finally, the multi-layer model is used to investigate the impact that clay/polyurethane nanocomposite diffusion barriers can have on VOC emissions. Indoor gas-phase concentrations can be greatly reduced with a barrier layer on the surface, thereby minimizing the environmental impact of SIPs.
Keywords: Diffusion; Emission; Fugacity; Multi-layer; Model; Volatile organic compound; Building material; Barrier layer; Indoor air;

Ambient aerosols adversely affect human health and visibility and impact climate. Identification of sources of particulate matter and its precursors is necessary for developing control strategies. The goal of this research is to utilize long-term speciated particulate matter data and back-trajectory cluster analyses to determine trends and sources of particulate matter in the Superstition Wilderness, a rural area east of Phoenix, Arizona. Twenty-four hour back-trajectories were calculated for every hour of every 24-h particulate matter sample obtained by IMPROVE from 1991 to 2004. Days that included back-trajectories with considerable spatial variance were excluded from further analyses. To minimize uncertainties inherent in single trajectories, all calculated trajectories for each sampling day were averaged to represent the air mass sampled during that day. Cluster analysis of trajectories identified four unique regions, including a region with Phoenix, a region with copper smelters, and one with coal-fired power plants. Yearly averages of sulfate, nitrate, soil, and carbon concentrations were calculated for each region. Statistically significant trends in species concentrations by region and independent of region and differences in concentrations between regions were examined.Sulfate concentrations from the region with smelters were higher than other regions but decreased during the study period. Emissions data from the smelters indicate that much of the sulfate from the region was due to the smelters. The overall 2.2% year−1 decrease in sulfate concentrations at TNM is likely due to decreased emissions from the copper smelters. A 3.6% year−1 increase in nitrate concentrations was driven largely by increasing NO x concentrations from Phoenix and to a lesser extent the region southwest of the site which includes Tucson and suburban/urban areas between Phoenix and Tucson. Soil concentrations were higher from regions with deserts than the region without desert. This method could not identify trends or source regions of carbonaceous aerosols at this site.
Keywords: Trajectories; Cluster analysis; IMPROVE; PM2.5 trends; Rural;

Photochemical production of ozone and control strategy for Southern Taiwan by Chein-Jung Shiu; Shaw Chen Liu; Chih-Chung Chang; Jen-Ping Chen; Charles C.K. Chou; Chuan-Yao Lin; Chea-Yuan Young (9324-9340).
An observation-based method (OBM) is developed to evaluate the ozone (O3) production efficiency (O3 molecules produced per NO x molecule consumed) and O3 production rate (P(O3)) during a field campaign in southern Taiwan. The method can also provide an estimate of the concentration of OH. A key step in the method is to use observed concentrations of two aromatic hydrocarbons, namely ethylbenzene and m,p-xylene, to estimate the degree of photochemical processing and amounts of photochemically consumed NO x and NMHCs by OH. In addition, total oxidant (O3+NO2) instead of O3 itself turns out to be very useful for representing ozone production in the OBM approach. The average O3 production efficiency during the field campaign in Fall (2003) is found to be about 10.2±3.9. The relationship of P(O3) with NO x is examined and compared with a one-dimensional (1D) photochemical model. Values of P(O3) derived from the OBM are slightly lower than those calculated in the 1D model. However, OH concentrations estimated by the OBM are about a factor of 2 lower than the 1D model. Fresh emissions, which affect the degree of photochemical processing appear to be a major cause of the underestimate. We have developed a three-dimensional (3D) OBM O3 production diagram that resembles the EKMA ozone isopleth diagram to study the relationship of the total oxidant versus O3 precursors. The 3D OBM O3 production diagram suggests that reducing emissions of NMHCs are more effective in controlling O3 than reducing NO x . However, significant uncertainties remain in the OBM, and considerable more work is required to minimize these uncertainties before a definitive control strategy can be reached. The observation-based approach provides a good alternative to measuring peroxy radicals for evaluating the production of O3 and formulating O3 control strategy in urban and suburban environments.
Keywords: Ozone; Precursors; Ozone production; Atmospheric oxidants; Ozone control strategy;

This work merges kinetic models for α-pinene and d-limonene which were individually developed to predict secondary organic aerosol (SOA) formation from these compounds. Three major changes in the d-limonene and α-pinene combined mechanism were made. First, radical–radical reactions were integrated so that radicals formed from both individual mechanisms all reacted with each other. Second, all SOA model species from both compounds were used to calculate semi-volatile partitioning for new semi-volatiles formed in the gas phase. Third particle phase reactions for particle phase α-pinene and d-limonene aldehydes, carboxylic acids, etc. were integrated. Experiments with mixtures of α-pinene and d-limonene, nitric oxide (NO), nitrogen dioxide (NO2), and diurnal natural sunlight were carried out in a dual 270 m3 outdoor Teflon film chamber located in Pittsboro, NC. The model closely simulated the behavior and timing for α-pinene, d-limonene, NO, NO2, O3 and SOA. Model sensitivities were tested with respect to effects of d-limonene/α-pinene ratios, initial hydrocarbon to NO x (HC0/NO x ) ratios, temperature, and light intensity. The results showed that SOA yield (Y SOA) was very sensitive to initial d-limonene/α-pinene ratio and temperature. The model was also used to simulate remote atmospheric SOA conditions that hypothetically could result from diurnal emissions of α-pinene, d-limonene and NO x . We observed that the volatility of the simulated SOA material on the aging aerosol decreased with time, and this was consistent with chamber observations. Of additional importance was that our simulation did not show a loss of SOA during the daytime and this was consistent with observed measurements.
Keywords: d-Limonene; α-Pinene; Kinetics mechanism; Model simulation; SOA;

This paper presents results from positive matrix factorization (PMF) of organic molecular marker data to investigate the sources of organic carbon (OC) in Pittsburgh, Pennsylvania. PMF analysis of 21 different combinations of input species found essentially the same seven factors with distinctive source-class-specific groupings of molecular markers. To link factors with source classes we directly compare PMF factor profiles with actual source profiles. Six of the PMF factors appear related to primary emissions from sources such as motor vehicles, biomass combustion, and food cooking. Each primary factor contributed between 5% and 10% of the annual-average OC with the exception of the cooking related factor which contributed 20% of the OC. However, the contribution of the cooking factor was sensitive to the specific combinations of input species. PMF could not differentiate between gasoline and diesel emissions, but the aggregate contribution of primary emissions from these two source classes is estimated to be less than 10% of the annual-average OC. One factor appears related to secondary organic aerosol based on its substantial contribution to biogenic oxidation products. This secondary factor contributed more than 50% of the summertime average OC. Reasonable agreement was observed between the PMF results and those of a previously published chemical mass balance (CMB) analysis of the same molecular marker dataset. Individual PMF factors are correlated with specific CMB sources, but systematic biases exist between the two estimates. These biases were generally within the uncertainty of the two estimates, but there is also evidence that PMF is not cleanly differentiating between source classes.
Keywords: Fine particulate matter; Organic carbon; Source apportionment; Receptor modeling;

Estimation and validation of PM2.5/PM10 exhaust and non-exhaust emission factors for practical street pollution modelling by Matthias Ketzel; Gunnar Omstedt; Christer Johansson; Ingo Düring; Mia Pohjola; Dietmar Oettl; Lars Gidhagen; Peter Wåhlin; Achim Lohmeyer; Mervi Haakana; Ruwim Berkowicz (9370-9385).
In order to carry out efficient traffic and air quality management, validated models and PM emission estimates are needed. This paper compares current available emission factor estimates for PM10 and PM2.5 from emission databases and different emission models, and validates these against eight high quality street pollution measurements in Denmark, Sweden, Germany, Finland and Austria.The data sets show large variation of the PM concentration and emission factors with season and with location. Consistently at all roads the PM10 and PM2.5 emission factors are lower in the summer month than the rest of the year. For example, PM10 emission factors are in average 5–45% lower during the month 6–10 compared to the annual average.The range of observed total emission factors (including non-exhaust emissions) for the different sites during summer conditions are 80–130 mg km−1 for PM10, 30–60 mg km−1 for PM2.5 and 20–50 mg km−1 for the exhaust emissions.We present two different strategies regarding modelling of PM emissions: (1) For Nordic conditions with strong seasonal variations due to studded tyres and the use of sand/salt as anti-skid treatment a time varying emission model is needed. An empirical model accounting for these Nordic conditions was previously developed in Sweden. (2) For other roads with a less pronounced seasonal variation (e.g. in Denmark, Germany, Austria) methods using a constant emission factor maybe appropriate. Two models are presented here.Further, we apply the different emission models to data sets outside the original countries. For example, we apply the “Swedish” model for two streets without studded tyre usage and the “German” model for Nordic data sets. The “Swedish” empirical model performs best for streets with studded tyre use, but was not able to improve the correlation versus measurements in comparison to using constant emission factors for the Danish side. The “German” method performed well for the streets without clear seasonal variation and reproduces the summer conditions for streets with pronounced seasonal variation. However, the seasonal variation of PM emission factors can be important even for countries not using studded tyres, e.g. in areas with cold weather and snow events using sand and de-icing materials. Here a constant emission factor probably will under-estimate the 90-percentiles and therefore a time varying emission model need to be used or developed for such areas.All emission factor models consistently indicate that a large part (about 50–85% depending on the location) of the total PM10 emissions originates from non-exhaust emissions. This implies that reduction measures for the exhaust part of the vehicle emissions will only have a limited effect on ambient PM10 levels.
Keywords: Particle mass; Vehicle emission factors; Urban road traffic; Re-suspension;

Spatial distribution and source identification of wet deposition at remote EANET sites in Japan by Sinya Seto; Manabu Sato; Tsutomu Tatano; Takashi Kusakari; Hiroshi Hara (9386-9396).
Wet deposition of major ions was discussed from the viewpoint of its potential sources for six remote EANET sites in Japan (Rishiri, Happo, Oki, Ogasawara, Yusuhara, and Hedo) having sufficiently high data completeness during 2000–2004. The annual deposition for each site ranged from 12.1 to 46.6 meq m−2  yr−1 for nss-SO4 2−, from 5.0 to 21.9 meq m−2  yr−1 for NO3 . The ranges of annual deposition of the two ions for the sites were lower than those for urban and rural sites in Japanese Acid Deposition Survey by Ministry of the Environment, Japan, and higher than those for global remote marine sites. Factor analysis was performed on log-transformed daily wet deposition of major ions for each site. The obtained two factors were interpreted as (1) acid and soil source (or acid source for some sites), and (2) sea-salt source for all the sites. This indicates that wet deposition of ions over the remote areas in Japan has a similar structure in terms of types of sources. Factor scores of acid and soil source were relatively high during Kosa (Asian dust) events in spring in western Japan. Back-trajectories for high-deposition episodes of acid and soil source (or acid source) for the remote sites showed that episodic air masses frequently came from the northeastern area of Asian Continent in spring and winter, and from central China in summer and autumn. This indicates a large contribution of continental emissions to wet deposition of ions over the remote areas in Japan.
Keywords: Acidic deposition; Back-trajectory; Factor analysis; Potential sources; East Asia;

Source characterization and identification by real-time single particle mass spectrometry by Melissa S. Reinard; Kouame Adou; Joseph M. Martini; Murray V. Johnston (9397-9409).
A Real-Time Single Particle Mass Spectrometer, RSMS-3, was deployed to Wilmington, Delaware to study regional and local contributions to fine and ultra-fine urban particulate matter (PM). Approximately two-thirds of PM1 consisted of internally mixed secondary aerosol. The remaining one-third was externally mixed including biomass burning (13%), fossil fuel combustion (7%) and various industrial sources (13%). In this last group, particle classes containing specific combinations of transition and/or heavy metals gave wind-rose plots consistent with specific point sources. For example, particles containing V and Ni were detected from different wind directions than those containing V and Fe. Samples from two industrial emission stacks, a steel manufacturing facility 10 km away and a coal-fired electrical power generation facility 5 km away, were analyzed and compared to the ambient data set. In each case, a direct correlation was found: a Pb–Zn–K–Na class for the steel manufacturing facility and an Fe–La/Ce class for the power generation facility. The ambient particle classes showed additional small signals from secondary components indicating atmospheric processing. Ambient particle classes containing only a subset of these elements, such as Zn only, Fe only and Pb–K only, were nonspecific, that is, the wind-rose plots were more diffuse and the particles could not be mapped to individual sources. The merits of stack sampling as an aid to interpreting single particle data sets are discussed.
Keywords: Urban aerosol; Single particle mass spectrometry; Metals; Lead; Stack emissions;

A hybrid modeling approach to resolve pollutant concentrations in an urban area by Ariel F. Stein; Vlad Isakov; James Godowitch; Roland R. Draxler (9410-9426).
A modeling tool that can resolve contributions from individual sources to the urban environment is critical for air-toxics exposure assessments. Air toxics are often chemically reactive and may have background concentrations originated from distant sources. Grid models are the best-suited tools to handle the regional features of these chemicals. However, these models are not designed to resolve pollutant concentrations on local scales. Moreover, for many species of interest, having reaction time scales that are longer than the travel time across an urban area, chemical reactions can be ignored in describing local dispersion from strong individual sources making Lagrangian and plume-dispersion models practical. In this study, we test the feasibility of developing an urban hybrid simulation system. In this combination, the Community Multi-scale Air Quality model (CMAQ) provides the regional background concentrations and urban-scale photochemistry, and local models such as Hybrid Single Particle Lagrangian Integrated Trajectory model (HYSPLIT) and AMS/EPA Regulatory Model (AERMOD) provide the more spatially resolved concentrations due to local emission sources. In the initial application, the HYSPLIT, AERMOD, and CMAQ models are used in combination to calculate high-resolution benzene concentrations in the Houston area. The study period is from 18 August to 4 September of 2000. The Mesoscale Model 5 (MM5) is used to create meteorological fields with a horizontal resolution of 1×1 km2. In another variation to this approach, multiple HYSPLIT simulations are used to create a concentration ensemble to estimate the contribution to the concentration variability from point sources. HYSPLIT simulations are used to model two sources of concentration variability; one due to variability created by different particle trajectory pathways in the turbulent atmosphere and the other due to different flow regimes that might be introduced when using gridded data to represent meteorological data fields. The ensemble mean concentrations determined by HYSPLIT plus the concentrations estimated by AERMOD are added to the CMAQ calculated background to estimate the total mean benzene concentration. These estimated hourly mean concentrations are also compared with available field measurements.
Keywords: Spatial variability; Air toxics; CMAQ; HYSPLIT; AERMOD;

Long-term study of air pollution plays a decisive role in formulating and refining pollution control strategies. In this study, two 12-month measurements of PM2.5 mass and speciation were conducted in 00/01 and 04/05 to determine long-term trend and spatial variations of PM2.5 mass and chemical composition in Hong Kong. This study covered three sites with different land-use characteristics, namely roadside, urban, and rural environments. The highest annual average PM2.5 concentration was observed at the roadside site (58.0±2.0 μg m−3 (average±2σ) in 00/01 and 53.0±2.7 μg m−3 in 04/05), followed by the urban site (33.9±2.5 μg m−3 in 00/01 and 39.0±2.0 μg m−3 in 04/05), and the rural site (23.7±1.9 μg m−3 in 00/01 and 28.4±2.4 μg m−3 in 04/05). The lowest PM2.5 level measured at the rural site was still higher than the United States’ annual average National Ambient Air Quality Standard of 15 μg m−3. As expected, seasonal variations of PM2.5 mass concentration at the three sites were similar: higher in autumn/winter and lower in summer. Comparing PM2.5 data in 04/05 with those collected in 00/01, a reduction in PM2.5 mass concentration at the roadside (8.7%) but an increase at the urban (15%) and rural (20%) sites were observed. The reduction of PM2.5 at the roadside was attributed to the decrease of carbonaceous aerosols (organic carbon and elemental carbon) (>30%), indicating the effective control of motor vehicle emissions over the period. On the other hand, the sulfate concentration at the three sites was consistent regardless of different land-use characteristics in both studies. The lack of spatial variation of sulfate concentrations in PM2.5 implied its origin of regional contribution. Moreover, over 36% growth in sulfate concentration was found from 00/01 to 04/05, suggesting a significant increase in regional sulfate pollution over the years. More quantitative techniques such as receptor models and chemical transport models are required to assess the temporal variations of source contributions to ambient PM2.5 mass and chemical speciation in Hong Kong.
Keywords: Long-term trends; PM2.5; Organic carbon; Elemental carbon; Sulfate; Nitrate;

A scanning transmission X-ray microscope at the Lawrence Berkeley National Laboratory is used to measure organic functional group abundance and morphology of atmospheric aerosols. We present a summary of spectra, sizes, and shapes observed in 595 particles that were collected and analyzed between 2000 and 2006. These particles ranged between 0.1 and 12 μm and represent aerosols found in a large range of geographical areas, altitudes, and times. They include samples from seven different field campaigns: PELTI, ACE-ASIA, DYCOMS II, Princeton, MILAGRO (urban), MILAGRO (C-130), and INTEX-B. At least 14 different classes of organic particles show different types of spectroscopic signatures. Different particle types are found within the same region while the same particle types are also found in different geographical domains. Particles chemically resembling black carbon, humic-like aerosols, pine ultisol, and secondary or processed aerosol have been identified from functional group abundance and comparison of spectra with those published in the literature.
Keywords: Aerosol; Microscopy; Carbonaceous aerosol; Organic; Functional group; NEXAFS; XANES; STXM;

Chemical composition of rainwater in the northeastern Romania, Iasi region (2003–2006) by Cecilia Arsene; Romeo Iulian Olariu; Nikolaos Mihalopoulos (9452-9467).
Chemical composition of rainwater was studied in the northeastern Romania, Iasi region, and the concentrations of major inorganic and organic ions were measured in samples collected between April 2003 and December 2006. The pH of the rainwater is 5.92 (volume weighted mean average, VWM) suggesting a sufficient load of alkaline components neutralizing its acidity. On average, 97% of the acidity in the collected samples is neutralized by CaCO3 and NH3. Clear seasonal variations were observed for some of the identified ions (e.g., SO4 2−, NO3 , Ca2+, NH4 +). The data obtained during this work revealed that both concentrations and fluxes of anthropogenic source-related ions (e.g., SO4 2−, NO3 and NH4 +) are among the highest reported for European sites. It is shown that meteorology and long-range transport processes may concur to their high levels.
Keywords: Rainwater; Ionic composition; Deposition flux; Romania;

Six years (1998–2003) of measurements of ambient air concentrations of total suspended particulate (TSP) measured at a rural background monitoring station in Tenerife (Canary Islands), the El Río station (ER, 28°08′35″N, 16°39′20″W, 500 m a.s.l.) were studied. African dust outbreaks were objectively identified using a new quantitative tool, called the African Index. This index indicates the percentage of time that an air mass remained over an African region at one of three possible height intervals of the lower troposphere. After identifying these episodes, a study of the background TSP levels at the ER station and of direct and indirect (those which cause vertical deposition of dust) African air mass intrusion impacts was performed. Taking into account both direct and indirect episodes, a total of 322 days of African dust intrusion were objectively identified (a mean of 54 episodes per year) in the period 1998–2003, some of them caused by “transition episodes” or “return African air masses”. A subjective method confirmed that 256 of these days were caused by direct impacts of African dust on the ER station. A mean TSP value of 21.6 μg m−3 was found at the station during this period. All the episodes occurred when the TSP concentration was >28.5 μg m−3. The TSP background (∼14 μg m−3) can be assumed to be representative of the MBL of the Eastern North Atlantic subtropical region. The highest number of dust gravitational settlement (or indirect) episodes occurs in summer, but the highest contribution of these episodes to the TSP levels is in March with a monthly mean TSP contribution of up to 30.5 μg m−3.
Keywords: African dust; Gravitational settlement; Marine boundary layer; Background levels;

Analysis of air quality data near roadways using a dispersion model by Akula Venkatram; Vlad Isakov; Eben Thoma; Richard Baldauf (9481-9497).
We used a dispersion model to analyze measurements made during a field study conducted by the U.S. EPA in July–August 2006, to estimate the impact of traffic emissions on air quality at distances of tens of meters from an eight-lane highway located in Raleigh, NC. The air quality measurements consisted of long path optical measurements of NO at distances of 7 and 17 m from the edge of the highway. Sonic anemometers were used to measure wind speed and turbulent velocities at 6 and 20 m from the highway. Traffic flow rates were monitored using traffic surveillance cameras. The dispersion model [Venkatram, A., 2004. On estimating emissions through horizontal fluxes. Atmospheric Environment 38, 2439–2446] explained over 60% of the variance of the observed path averaged NO concentrations, and over 90% of the observed concentrations were within a factor of two of the model estimates.Sensitivity tests conducted with the model indicated that the traffic flow rate made the largest contribution to the variance of the observed NO concentrations. The meteorological variable that had the largest impact on the near road NO concentrations was the standard deviation of the vertical velocity fluctuations, σ w. Wind speed had a relatively minor effect on concentrations. Furthermore, as long as the wind direction was within ±45° from the normal to the road, wind direction had little impact on near road concentrations. The measurements did not allow us to draw conclusions on the impact of traffic-induced turbulence on dispersion. The analysis of air quality and meteorological observations resulted in plausible estimates of on-road emission factors for NO.
Keywords: Air quality; Line source; Dispersion modeling; Traffic emissions; Mobile sources;

Croplands contribute to atmospheric nitric oxide (NO), but very limited data are available about NO fluxes from intensively managed croplands in China. In this study, NO fluxes were measured in a typical vegetable field planted with flowering Chinese cabbage (Brassica campestris L. ssp. Chinensis var. utilis Tsen et Lee), which is the most widely cultivated vegetable in Guangdong province, south China. NO emission drastically increased after nitrogen fertilizer application, and other practices involving loosening the soil also enhanced NO emission. Mean NO emission flux was 47.5 ng N m−2  s–1 over a complete growth cycle. Annual NO emission from the vegetable field was about 10.1 kg N ha−1  yr−1. Fertilizer-induced NO emission factor was estimated to be 2.4%. Total NO emission from vegetable fields in Guangdong province was roughly estimated to be 11.7 Gg N yr−1 based on the vegetable field area and annual NO emission rate, and to be 13.3 Gg N yr−1 based on fertilizer-induced NO emission factor and background NO emission. This means that NO emission from vegetable fields was approximately 6% of NO x from commercial energy consumption in Guangdong province.
Keywords: Nitric oxide; Emission flux; Cropland; China;

The dispersion of the Buncefield oil fire plume: An extreme accident without air quality consequences by R. Vautard; P. Ciais; R. Fisher; D. Lowry; F.M. Bréon; F. Vogel; I. Levin; F. Miglietta; E. Nisbet (9506-9517).
The dispersion of pollutants from the huge Buncefield oil depot fire that occurred on 11 December 2005 is simulated using a regional Eulerian chemistry-transport model. We analyse the transport and mixing of the fire plume. We show that the hot plume never reached the ground. Instead, it pierced the thin wintertime boundary layer and was injected into the free troposphere at higher altitudes. This is in agreement with data from many air quality stations. This high injection was fortunate because the fine aerosol particles (PM10) mass column generated by the fire smoke exceeded that of ordinary pollution by an order of magnitude. Our regional chemistry-transport modelling is able to predict the early development of the plume dispersion, as shown by a qualitative comparison between simulated PM10 columns and a satellite image obtained by the EOS-TERRA-MODIS sensor.If the accident had occurred in summer when boundary layers are much deeper and convective, a severe degradation in air quality due to PM10 could have occurred, as shown by a sensitivity simulation assuming a similar fire during one of the hottest days of August 2003. The modelled impact of the fire on regional and European air quality levels strongly depends on the altitude reached by the buoyant plume, as shown by a set of sensitivity simulations with variable injection heights. However, in all cases we found that the fire only affected surface aerosol concentrations without increasing photochemical pollution.
Keywords: Buncefield; Smoke plume; Air quality; Transport model; Particulate matter;

Relationships between indoor and outdoor air pollution by carcinogenic PAHs and PCBs by E. Menichini; N. Iacovella; F. Monfredini; L. Turrio-Baldassarri (9518-9529).
PAHs and PCBs were collected simultaneously indoors and outdoors at eight non-smoking homes located in four buildings in high-traffic areas of Rome. The purpose was to evaluate the relevance of indoor air in contributing to the overall exposure of the urban population. The vertical distribution was also investigated by collecting outdoor samples at both road and roof level, and indoor samples in both a high and a low floor flat of each building. At one coal-heated building, samples were collected during both the heating and the non-heating season. No evident PAH source was present indoors. Indoor and outdoor daily concentrations of benzo[a]pyrene (BaP) ranged, respectively, 0.1–4.6 ng m−3 and 0.7–2.3 ng m−3. With the heating on, indoor PAH concentrations equalled or exceeded those outdoors, with BaP indoor/outdoor ratios up to 4; during the warm season, ratios decreased to 0.2–0.6. Indoor PAHs at the low floors exceeded the high-floor ones when the heating was off (vehicle exhausts being the dominant source), while being equal or lower with the heating on; the vertical gradient of indoor PAHs between different floors was within a factor of 2. Outdoor PAHs at roof level were 20–70% of those at road level, which in turn exceeded those at the medium-traffic station up to a factor of 4. The outdoor concentrations of Σ6 indicator PCBs ranged 0.1–1.6 ng m−3. Indoor PCB concentrations exceeded those outdoors by an approximate factor of 2–50. No vertical gradient was observed. The results indicated that indoor air may contribute to the overall exposure to PAHs and PCBs more than the urban air. They were also consistent with recent findings suggesting that indoor air can be a relevant source of PCBs for outdoor air.
Keywords: BaP; Benzo[a]pyrene; Coal-fuelled heating; I/O ratio; Vertical gradient;

Influence of indoor transport and mixing time scales on the performance of sensor systems for characterizing contaminant releases by Priya Sreedharan; Michael D. Sohn; William W Nazaroff; Ashok J. Gadgil (9530-9542).
Optimizing real-time sensor systems to detect and identify relevant characteristics of an indoor contaminant event is a challenging task. The interpretation of incoming sensor data is confounded by uncertainties in building operation, in the forces driving contaminant transport, and in the physical parameters governing transport. In addition, simulation tools used by the sensor interpretation algorithm introduce modeling uncertainties. This paper explores how the time scales inherent in contaminant transport influence the information that can be extracted from real-time sensor data. In particular, we identify three time scales (within room mixing, room-to-room transport, and removal from the building) and study how they affect the ability of a Bayesian Monte Carlo (BMC) sensor interpretation algorithm to identify the release location and release mass from a set of experimental data, recorded in a multi-floor building. The research shows that some limitations in the BMC approach do not depend on details of the models or the algorithmic implementation, but rather on the physics of contaminant transport. These inherent constraints have implications for the design of sensor systems.
Keywords: Sensor system; Multizone model; Contaminant transport; Inverse problem; Bayes Monte Carlo; Buildings; Time scales;

Assessment of yield losses in tropical wheat using open top chambers by R. Rai; M. Agrawal; S.B. Agrawal (9543-9554).
The present study deals with the evaluation of effects of ambient gaseous air pollution on wheat (Triticum aestivum L. var. HUW-234) growing in a suburban area situated in eastern Gangetic plain of India, using open top chambers. Eight hourly air monitoring was conducted for ambient concentrations of SO2, NO2 and O3 in filtered chambers (FCs), non-filtered chambers (NFCs) and open plots (OPs). Various morphological, physiological and biochemical parameters were assessed during different developmental stages and finally yield parameters were quantified at the time of harvest.Mean concentrations of SO2, NO2 and O3 were 8.4, 39.9 and 40.1 ppb, respectively during the experiment in NFCs. Concentrations of SO2, NO2 and O3 reduced by 74.6%, 84.7% and 90.4%, respectively in FCs as compared to NFCs. Plants grown in FCs showed higher photosynthetic rate, stomatal conductance, chlorophyll content and Fv/Fm ratio as compared to the plants in NFCs and OPs. Lipid peroxidation, proline, total phenol and ascorbic acid contents and peroxidase activity were higher in plants grown in NFCs. There were improvements in morphological parameters of plants growing in FCs as compared to those in NFCs and OPs. Yield of plants also increased significantly in FCs as compared to those ventilated with ambient air (NFCs) or grown in OPs. During the vegetative phase, NO2 concentrations were higher than O3, but O3 became dominant pollutant during the time of grain setting and filling. The study concludes that O3 and NO2 are the main air pollutants in the sub-urban areas causing significant yield reductions in tropical wheat plants.
Keywords: Open top chambers; Ozone; Sulphur dioxide; Nitrogen dioxide; Effects; Wheat;

Assessment and prediction of exposure to benzene of filling station employees by Spyros P. Karakitsios; Costas L. Papaloukas; Pavlos A. Kassomenos; Georgios A. Pilidis (9555-9569).
In the present study, the exposure to benzene of employees working in two filling stations (one urban and one rural) was estimated, through the method of passive sampling. Additional data (30′ measurements of benzene exposure through active sampling to employees dealing with different activities, meteorological and traffic data) were collected. The measurements campaign was performed in both summer and wintertime to determine the seasonal variation of the exposure pattern.In addition, a set of artificial neural networks (ANNs) was developed to predict benzene exposure pattern for the filling station employees based on active sampling data and the parameters related to the employees’ exposure. The quantification of the contribution of each parameter to the overall exposure pattern was also attempted.The results showed that although vapour recovery technologies are installed in the refuelling systems and benzene emissions are significantly reduced compared to the past, filling station employees are still highly exposed to benzene (52–15 μg m−3). Benzene exposure is strongly correlated to car refuelling (exposure levels up to 85 μg m−3), while activities like car washing or working in cash machine inside an office contribute to lower exposure levels (up to 44 and 24 μg m−3 respectively). In rural filling station, exposure levels were in general lower compared to the urban ones, due to the smaller amount of gasoline that was traded and the absence of any significant traffic effect or urban background concentration. The developed ANN seemed to be a promising technique in the prediction of the exposure pattern giving very good results, and the quantification of the parameters affirmed the importance of the refueling procedure to the exposure levels.
Keywords: Benzene; Filling stations; ANN; Human exposure;

Total column abundances of CO, HCN, C2H6, and C2H2 have been retrieved from infrared solar spectra observed at Moshiri (44.4°N) and Rikubetsu (43.5°N) in northern Japan from 1997 to 2005. The spectra were recorded with high spectral resolution ground-based Fourier transform infrared (FTIR) spectrometers and total column abundances were calculated by SFIT1 version 1.09e. Deviations of these species relative to their seasonal mean values (ΔCO, ΔHCN, ΔC2H6, and ΔC2H2) were derived, which showed short-time enhancements in 1998, 2002, and 2003. Good correlations among ΔCO, ΔHCN, ΔC2H6, and ΔC2H2 in a few months of each year were seen. Since the number of forest fires in Siberia had large enhancements in 1998, 2002, and 2003, trajectory analyses were performed in order to assess the influence of forest fires and it was confirmed that air masses passing over the location of burning points in Siberia reached Moshiri and Rikubetsu. This paper shows that enhancements of these species were driven by biomass burning in Siberia.
Keywords: Emission enhancement; Siberia forest fires; FTIR; Backward trajectory;

The effect of variability in industrial emissions on ozone formation in Houston, Texas by Mort Webster; Junsang Nam; Yosuke Kimura; Harvey Jeffries; William Vizuete; David T. Allen (9580-9593).
Ambient observations have indicated that high concentrations of ozone observed in the Houston/Galveston area are associated with plumes of highly reactive hydrocarbons, mixed with NO x , from industrial facilities. Ambient observations and industrial process data, such as mass flow rates for industrial flares, indicate that the VOCs associated with these industrial emissions can have significant temporal variability. To characterize the effect of this variability in emissions on ozone formation in Houston, data were collected on the temporal variability of industrial emissions or emission surrogates (e.g., mass flow rates to flares). The observed emissions variability was then used to construct regionwide emission inventories with variable industrial emissions, and the impacts of the variability on ozone formation were examined for two types of meteorological conditions, both of which lead to high ozone concentrations in Houston. The air quality simulations indicate that variability in industrial emissions has the potential to cause increases and decreases of 10–52 ppb (13–316%), or more, in ozone concentration. The largest of these differences are restricted to regions of 10–20 km2, but the variability also has the potential to increase regionwide maxima in ozone concentrations by up to 12 ppb.
Keywords: Photochemical grid model; Highly reactive volatile organic compounds (HRVOCs); Ozone; Uncertainty analysis; Monte Carlo simulation;

Vertical distribution of polycyclic aromatic hydrocarbons in atmospheric boundary layer of Beijing in winter by Shu Tao; Yi Wang; Shiming Wu; Shuzheng Liu; Han Dou; Yanan Liu; Chang Lang; Fei Hu; Baoshan Xing (9594-9602).
Air samples were collected using active samplers at various heights of 8, 15, 32, 47, 65, 80, 102, 120, 140, 160, 180, 200, 240, 280 and 320 m on a meteorological tower in an urban area of Beijing in two campaigns in winter 2006. Altitudinal distributions of polycyclic aromatic hydrocarbons (PAHs) in atmospheric boundary layer of Beijing in winter season were investigated. Meteorological conditions during the studied period were characterized by online measurements of four meteorological parameters as well as trajectory calculation. The mean total concentrations of 15 PAHs except naphthalene of gaseous and particulate phase were 667±450 and 331±144 ng m−3 in January and 61±19 and 29±6 ng m−3 in March, respectively. Domestic coal combustion and vehicle emission were the dominant PAH sources in winter. Although the composition profiles derived from the two campaigns were similar, the concentrations were different by one order of magnitude. The higher concentrations in January were partly caused by higher emission due to colder weather than March. Moreover, weak wind, passing through the city center before the sampling site, picked up more contaminants on the way and provided unfavorable dispersion condition in January. For both campaigns, PAH concentrations decreased with heights because of ground-level emission and unfavorable dispersion conditions in winter. The concentration ratio of PAHs in gas versus solid phases was temperature dependent and negatively correlated to their octanol–air partition coefficients.
Keywords: Atmosphere; PAHs; Vertical distribution; Trajectory; Beijing;

Evaluation of the Community Multiscale Air Quality (CMAQ) model version 4.5: Sensitivities impacting model performance by K. Wyat Appel; Alice B. Gilliland; Golam Sarwar; Robert C. Gilliam (9603-9615).
This study examines ozone (O3) predictions from the Community Multiscale Air Quality (CMAQ) model version 4.5 and discusses potential factors influencing the model results. Daily maximum 8-h average O3 levels are largely underpredicted when observed O3 levels are above 85 ppb and overpredicted when they are below 35 ppb. Using a clustering approach, model performance was examined separately for several different synoptic regimes. Under the most common synoptic conditions of a typical summertime Bermuda High setup, the model showed good overall performance for O3, while associations have been identified here between other, less frequent, synoptic regimes and the O3 overprediction and underprediction biases. A sensitivity test between the CB-IV and CB05 chemical mechanisms showed that predictions of daily maximum 8-h average O3 using CB05 were on average 7.3% higher than those using CB-IV. Boundary condition (BC) sensitivity tests show that the overprediction biases at low O3 levels are more sensitive to the BC O3 levels near the surface than BC concentrations aloft. These sensitivity tests also show the model performance for O3 improved when using the global GEOS-CHEM BCs instead of default profiles. Simulations using the newest version of the CMAQ model (v4.6) showed a small improvement in O3 predictions, particularly when vertical layers were not collapsed. Collectively, the results suggest that key synoptic weather patterns play a leading role in the prediction biases, and more detailed study of these episodes are needed to identify further modeling improvements.
Keywords: Air quality model; Community Multiscale Air Quality (CMAQ) model; Model evaluation; Ozone; Synoptic cluster;

The chemical mass balance (CMB) model was applied for source apportionment of PM2.5 in Atlanta in order to explore levels and causes of uncertainties in source contributions. Monte Carlo analysis with Latin hypercube sampling (MC-LHS) was performed to evaluate the source impact uncertainties and quantify how uncertainties in ambient measurement and source profile data affect results. In general, uncertainties in the source profile data contribute more to the final uncertainties in source apportionment results than do those in ambient measurement data. Uncertainty contribution estimates suggest that non-linear interactions among source profiles also affect the final uncertainties although their influence is typically less than uncertainties in source profile data.
Keywords: CMB; PM2.5; Uncertainty; Monte Carlo analysis;