Atmospheric Environment (v.44, #39)

The likely health and environmental implications associated with atmospheric nanoparticles have prompted considerable recent research activity. Knowledge of the characteristics of these particles has improved considerably due to an ever growing interest in the scientific community, though not yet sufficient to enable regulatory decision making on a particle number basis. This review synthesizes the existing knowledge of nanoparticles in the urban atmosphere, highlights recent advances in our understanding and discusses research priorities and emerging aspects of the subject. The article begins by describing the characteristics of the particles and in doing so treats their formation, chemical composition and number concentrations, as well as the role of removal mechanisms of various kinds. This is followed by an overview of emerging classes of nanoparticles (i.e. manufactured and bio-fuel derived), together with a brief discussion of other sources. The subsequent section provides a comprehensive review of the working principles, capabilities and limitations of the main classes of advanced instrumentation that are currently deployed to measure number and size distributions of nanoparticles in the atmosphere. A further section focuses on the dispersion modelling of nanoparticles and associated challenges. Recent toxicological and epidemiological studies are reviewed so as to highlight both current trends and the research needs relating to exposure to particles and the associated health implications. The review then addresses regulatory concerns by providing an historical perspective of recent developments together with the associated challenges involved in the control of airborne nanoparticle concentrations. The article concludes with a critical discussion of the topic areas covered.
Keywords: Airborne nanoparticles; Bio-fuel; Manufactured nanomaterials; Number and size distributions; Street canyons; Ultrafine particles;

Global comparison of VOC and CO observations in urban areas by Erika von Schneidemesser; Paul S. Monks; Christian Plass-Duelmer (5053-5064).
Speciated volatile organic compound (VOC) and carbon monoxide (CO) measurements from the Marylebone Road site in central London from 1998 through 2008 are presented. Long-term trends show statistically significant decreases for all the VOCs considered, ranging from −3% to −26% per year. Carbon monoxide decreased by −12% per year over the measurement period. The VOC trends observed at the kerbside site in London showed greater rates of decline relative to trends from monitoring sites in rural England (Harwell) and a remote high-altitude site (Hohenpeissenberg), which showed decreases for individual VOCs from −2% to −13% per year. Over the same 1998 through 2008 period VOC to CO ratios for London remained steady, an indication that emissions reduction measures affected the measured compounds equally. Relative trends comparing VOC to CO ratios between Marylebone Road and Hohenpeissenberg showed greater similarities than absolute trends, indicating that emissions reductions measures in urban areas are reflected by regional background locations. A comparison of VOC mixing ratios and VOC to CO ratios was undertaken for London and other global cities. Carbon monoxide and VOCs (alkanes greater than C5, alkenes, and aromatics) were found to be strongly correlated (>0.8) in the Annex I countries, whereas only ethene and ethyne were strongly correlated with CO in the non-Annex I countries. The correlation results indicate significant emissions from traffic-related sources in Annex I countries, and a much larger influence of other sources, such as industry and LPG-related sources in non-Annex I countries. Yearly benzene to ethyne ratios for London from 2000 to 2008 ranged from 0.17 to 0.29 and compared well with previous results from US cities and three global megacities.
Keywords: Volatile organic compounds; Long-term trends; Urban; Carbon monoxide;

Food wastes collected from typical urban residential communities were investigated for the emission of volatile organic sulfur compounds (VOSCs) during laboratory-controlled aerobic decomposition in an incubator for a period of 41 days. Emission of VOSCs from the food wastes totaled 409.9 mg kg−1 (dry weight), and dimethyl disulfide (DMDS), dimethyl sulfide (DMS), methyl 2-propenyl disulfide, carbonyl sulfide and methyl 1-propenyl sulfide were the five most abundant VOSCs, with shares of 75.5%, 13.5%, 4.8%, 2.2% and 1.3% in total 15 VOSCs released, respectively. The emission fluxes of major VOSCs were very low at the beginning (day 0). They peaked at days 2–4 and then decreased sharply until they leveled off after 10 days of incubation. For most VOSCs, over 95% of their emission occurred in the first 10 days. The time series of VOSC emission fluxes, as well as their significant correlation with internal food waste temperature (p  < 0.05) during incubation, suggested that production of VOSC species was induced mainly by microbial activities during the aerobic decomposition instead of as inherited. Released VOSCs accounted for 5.3% of sulfur content in the food wastes, implying that during aerobic decomposition considerable portion of sulfur in food wastes would be released into the atmosphere as VOSCs, primarily as DMDS, which is very short-lived in the atmosphere and thus usually less considered in the sources and sinks of reduced sulfur gases.
Keywords: Volatile organic sulfur compounds (VOSCs); Reduced sulfur gases; Aerobic decomposition; Food waste; Emission flux; Dimethyl sulfide (DMS); Dimethyl disulfide (DMDS);

An urban emissions inventory for South America and its application in numerical modeling of atmospheric chemical composition at local and regional scales by Marcelo Felix Alonso; Karla Maria Longo; Saulo R. Freitas; Rafael Mello da Fonseca; Virginie Marécal; Michel Pirre; Laura Gallardo Klenner (5072-5083).
This work describes the development of an urban vehicle emissions inventory for South America, based on the analysis and aggregation of available inventories for major cities, with emphasis on its application in regional atmospheric chemistry modeling. Due to the limited number of available local inventories, urban emissions were extrapolated based on the correlation between city vehicle density and mobile source emissions of carbon monoxide (CO) and nitrogen oxides (NOx). Emissions were geographically distributed using a methodology that delimits urban areas using high spatial resolution remote sensing products. This numerical algorithm enabled a more precise representation of urban centers. The derived regional inventory was evaluated by analyzing the performance of a chemical weather forecast model in relation to observations of CO, NOx and O3 in two different urban areas, São Paulo and Belo Horizonte. The gas mixing ratios simulated using the proposed regional inventory show good agreement with observations, consistently representing their hourly and daily variability. These results show that the integration of municipal inventories in a regional emissions map and their precise distribution in fine scale resolutions are important tools in regional atmospheric chemistry modeling.
Keywords: South American megacities; Urban emissions; Chemical weather forecasting; CCATT-BRAMS;

Emissions of volatile fatty acids from feed at dairy facilities by Phillip Alanis; Shawn Ashkan; Charles Krauter; Sean Campbell; Alam S. Hasson (5084-5092).
Recent studies suggest that dairy operations may be a major source of non-methane volatile organic compounds in dairy-intensive regions such as Central California, with short chain carboxylic acids (volatile fatty acids or VFAs) as the major components. Emissions of four VFAs (acetic acid, propanoic acid, butanoic acid and hexanoic acid) were measured from two feed sources (silage and total mixed rations (TMR)) at six Central California Dairies over a fifteen-month period. Measurements were made using a combination of flux chambers, solid phase micro-extraction fibers coupled to gas chromatography mass spectrometry (SPME/GC–MS) and infra-red photoaccoustic detection (IR-PAD for acetic acid only). The relationship between acetic acid emissions, source surface temperature and four sample composition factors (acetic acid content, ammonia-nitrogen content, water content and pH) was also investigated. As observed previously, acetic acid dominates the VFA emissions. Fluxes measured by IR-PAD were systematically lower than SPME/GC–MS measurements by a factor of two. High signals in field blanks prevented emissions from animal waste sources (flush lane, bedding, open lot) from being quantified. Acetic acid emissions from feed sources are positively correlated with surface temperature and acetic acid content. The measurements were used to derive a relationship between surface temperature, acetic acid content and the acetic acid flux. The equation derived from SPME/GC–MS measurements predicts estimated annual average acetic acid emissions of (0.7 + 1/−0.4) g m−2  h−1 from silage and (0.2 + 0.3/−0.1) g m−2  h−1 from TMR using annually averaged acetic acid content and meteorological data. However, during the summer months, fluxes may be several times higher than these values.
Keywords: Cattle; Flux measurements; Ozone precursors; California; Silage; VOC;

Corona ion induced atmospheric potential gradient perturbations near high voltage power lines by James C. Matthews; Jonathan P. Ward; Paul A. Keitch; Denis L. Henshaw (5093-5100).
High voltage power lines are known to produce corona ions that can be carried from the line by the wind, progressively attaching to ambient aerosol particles and causing fluctuations in the Earth’s atmospheric potential gradient. A fixed site monitoring station was installed near two power lines, which recorded the potential gradient at 1 s intervals and the ambient weather conditions every 10 min. The station ran continuously from January 2007 to December 2008, accumulating long-term data. Results from 2008 show an increase in potential gradient variability when a wind is blowing across the power lines towards the station, indicating that corona ions may be present in this environment.
Keywords: Corona ions; Space charge; Atmospheric electricity; Power lines;

Forecasting daily pollen concentrations using data-driven modeling methods in Thessaloniki, Greece by Dimitris Voukantsis; Harri Niska; Kostas Karatzas; Marina Riga; Athanasios Damialis; Despoina Vokou (5101-5111).
Airborne pollen have been associated with allergic symptoms in sensitized individuals, having a direct impact on the overall quality of life of a considerable fraction of the population. Therefore, forecasting elevated airborne pollen concentrations and communicating this piece of information to the public are key issues in prophylaxis and safeguarding the quality of life of the overall population. In this study, we adopt a data-oriented approach in order to develop operational forecasting models (1–7 days ahead) of daily average airborne pollen concentrations of the highly allergenic taxa: Poaceae, Oleaceae and Urticaceae. The models are developed using a representative dataset consisting of pollen and meteorological time-series recorded during the years 1987–2002, in the city of Thessaloniki, Greece. The input variables (features) of the models have been optimized by making use of genetic algorithms, whereas we evaluate the performance of three algorithms: i) multi-Layer Perceptron, ii) support vector regression and iii) regression trees originating from distinct domains of Computational Intelligence (CI), and compare the resulting models with traditional multiple linear regression models. Results show the superiority of CI methods, especially when forecasting several days ahead, compared to traditional multiple linear regression models. Furthermore, the CI models complement each other, resulting to a combined model that performs better than each one separately. The overall performance ranges, in terms of the index of agreement, from 0.85 to 0.93 clearly suggesting the potential operational use of the models. The latter ones can be utilized in provision of personalized and on-time information services, which can improve quality of life of sensitized citizens.
Keywords: Allergy; Feature selection; Forecasting; Genetic algorithms; Neural networks; Regression trees; Support vector machines;

A simplified approach to the indirect evaluation of the chemical composition of atmospheric aerosols from PM mass concentrations by Jorge Pey; Andrés Alastuey; Xavier Querol; Noemí Pérez; Michael Cusack (5112-5121).
The present work shows a straightforward procedure to indirectly estimate the chemical composition at a given site only from the determination of the PM concentrations, and the classification of the days according to the main meteorological scenarios. A previous study based on the mean chemical composition associated to the main meteorological scenarios is required.This experiment has been carried out with data from two monitoring sites in the North-Western Mediterranean, one regional and one suburban background. At both sites, one-year datasets on chemical PM10 composition were obtained. Based on these datasets, the mean PM10 compositions according to the most relevant meteorological situations were calculated for both locations. After that, the reconstruction of the chemical composition for all the days with available PM10 concentrations was completed. Subsequently, the estimated PM10 composition was compared with that determined experimentally. The comparison between the rebuilt and the experimental results was very satisfactory in the case of the regional background site, and relatively replaced in the other case. Furthermore, the validation of the method at the regional background site has been conducted from the reconstruction of a 4-year data base, and subsequent comparison with the experimental chemical composition.Our results show that it is possible to attain a good approach to the chemical composition at regional background sites, where local emission sources are negligible. Conversely, when the local sources rise in importance, i.e., at a suburban background site, the approach is suitable only for those components with a more regional origin and/or those from long range transport of air masses.
Keywords: Western Mediterranean; Modelling; Regional background; Mineral matter; PM10;

Data sets obtained from the quantitative analysis of 43 volatile organic compounds in air samples acquired every hour in 50 different sampling days (covering the different seasons) during the years 2005 and 2006 in a suburban area of the NW Spain have been investigated by different chemometric methods including matrix augmentation principal component analysis (MA-PCA) and parallel factor analysis (PARAFAC). The application of these two chemometric methods allowed the estimation of the chemical profiles of the main pollution sources operating over the investigated location and also unravelling their main temporal patterns. Using PCA, it was possible to identify four main different sources related to different VOC families (aromatic, aliphatic, halogenated and biogenic). However, the temporal emission patterns could not be properly resolved when the data of each individual sampling day were considered separately. When VOC emissions during the same week and for the whole year (50 sampling days) were simultaneously analysed by a new matrix augmentation PCA (MA-PCA) strategy and by PARAFAC, a better recovery and description of the daily and hourly temporal trends were achieved. In fact, the combination of MA-PCA with the score rearrangement followed by the first singular value decomposition allowed the extraction of daily cyclical emission trends that were subjacent in the original non-trilinear data matrix by means of a very simple methodology facilitating the interpretation of these complex data sets.
Keywords: Chemometrics; PCA; MA-PCA; PARAFAC; VOCs;

PM2.5 and PM10: The influence of sugarcane burning on potential cancer risk by Flavio S. Silva; Joyce Cristale; Paulo A. André; Paulo H.N. Saldiva; Mary R.R. Marchi (5133-5138).
In Brazil, sugarcane fields are often burned to facilitate manual harvesting, and this burning causes environmental pollution from the large amounts of soot released into the atmosphere. This material contains numerous organic compounds such as PAHs. In this study, the concentrations of PAHs in two particulate-matter fractions (PM2.5 and PM10) in the city of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugarcane plantations) were determined during the sugarcane harvest (HV) and non-harvest (NHV) seasons in 2008 and 2009. The sampling strategy included four campaigns, with 60 samples in the NHV season and 220 samples in the HV season. The PM2.5 and PM10 fractions were collected using a dichotomous sampler (10 L min−1, 24 h) with Teflon™ filters. The filter sets were extracted (ultrasonic bath with hexane/acetone (1:1 v/v)) and analyzed by HPLC/Fluorescence. The median concentration for total PAHs (PM2.5 in 2009) was 0.99 ng m−3 (NHV) and 3.3 ng m−3 (HV). In the HV season, the total concentration of carcinogenic PAHs (benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene) was 5 times higher than in the NHV season. B(a)P median concentrations were 0.017 ng m−3 and 0.12 ng m−3 for the NHV and HV seasons, respectively. The potential cancer risk associated with exposure through inhalation of these compounds was estimated based on the benzo[a]pyrene toxic equivalence (BaPeq), where the overall toxicity of a PAH mixture is defined by the concentration of each compound multiplied by its relative toxic equivalence factor (TEF). BaPeq median (2008 and 2009 years) ranged between 0.65 and 1.0 ng m−3 and 1.2–1.4 ng m−3 for the NHV and HV seasons, respectively. Considering that the maximum permissible BaPeq in ambient air is 1 ng m−3, related to the increased carcinogenic risk, our data suggest that the level of human exposure to PAHs in cities surrounded by sugarcane crops where the burning process is used is cause for concern.
Keywords: Polycyclic aromatic hydrocarbons (PAHs); benzo[a]pyrene toxic equivalence; Biomass burning; Cluster analysis; Principal components analysis;

Vertical transport of accumulation mode particles between two street canyons and the urban boundary layer by J.A. Salmond; L. Pauscher; G. Pigeon; V. Masson; D. Legain (5139-5147).
Concentrations and turbulent fluxes of accumulation mode particles were measured during the 2004–2005 ‘Canopy and Aerosol Particle Interaction in Toulouse Urban Layer’ project (CAPITOUL) at the top of two intersecting street canyons and in the urban boundary layer (UBL) in Toulouse, France. Particle numbers were strongly affected by boundary layer depth and showed limited sensitivity to local emissions. Differences in the diurnal patterns of particle numbers were observed between the finer fraction (0.3–0.4 μm) and coarser fraction (1.6–2.0 μm) of accumulation mode particles, indicating different processes of formation, evolution and transportation may be dominant. Highest particle numbers were observed in the narrow street canyon which had more limited local emissions and comparatively small particle fluxes. However, the improved ventilation rate in the wider canyon was also associated with the downward mixing of particles into the street canyon from the UBL. The results from this study clearly illustrate the temporal and spatial variability of particle numbers and fluxes in the urban atmosphere.
Keywords: Turbulent fluxes; Accumulation mode particles; Urban canopy layer; Urban boundary layer; Particle fluxes; Toulouse France;

Seasonal variations of monosaccharide anhydrides in PM1 and PM2.5 aerosol in urban areas by K. Křůmal; P. Mikuška; M. Vojtěšek; Z. Večeřa (5148-5155).
The concentrations of monosaccharide anhydrides (levoglucosan, mannosan, galactosan) in PM1 and PM2.5 aerosol samples were measured in Brno and Šlapanice in the Czech Republic in winter and summer 2009. 56 aerosol samples were collected together at both sites to investigate the different sources that contribute to aerosol composition in studied localities. Daily PM1 and PM2.5 aerosol samples were collected on pre-fired quartz fibre filters.The sum of average atmospheric concentration of levoglucosan, mannosan and galactosan in PM1 aerosol in Šlapanice and Brno during winter was 513 and 273 ng m−3, while in summer the sum of average atmospheric concentration of monosaccharide anhydrides (MAs) was 42 and 38 ng m−3, respectively. The sum of average atmospheric concentration of MAs in PM1 aerosol formed 71 and 63% of the sum of MA concentration in PM2.5 aerosol collected in winter in Šlapanice and Brno, whereas in summer the sum of average atmospheric concentration of MAs in PM1 aerosol formed 45 and 43% of the sum of MA concentration in PM2.5 aerosol in Šlapanice and Brno, respectively.In winter, the sum of MAs contributed significantly to PM1 mass ranging between 1.37% and 2.67% of PM1 mass (Brno – Šlapanice), while in summer the contribution of the sum of MAs was smaller (0.28–0.32%). Contribution of the sum of MAs to PM2.5 mass is similar both in winter (1.37–2.71%) and summer (0.44–0.55%).The higher concentrations of monosaccharide anhydrides in aerosols in Šlapanice indicate higher biomass combustion in this location than in Brno during winter season. The comparison of levoglucosan concentration in PM1 and PM2.5 aerosol shows prevailing presence of levoglucosan in PM1 aerosol both in winter (72% on average) and summer (60% on average).The aerosol samples collected in Šlapanice and Brno in winter and summer show comparable contributions of levoglucosan, mannosan and galactosan to the total amount of monosaccharide anhydrides in both aerosol size fractions. Levoglucosan was the most abundant monosaccharide anhydride with a relative average contribution to the total amount of MAs in the range of 71–82% for PM1 aerosols and 52–79% for PM2.5 aerosols.
Keywords: Monosaccharide anhydrides; Biomass burning; Levoglucosan; Mannosan; Galactosan; Czech Republic;

Modeling effects of traffic and landscape characteristics on ambient nitrogen dioxide levels in Connecticut by Katherine J. Skene; Janneane F. Gent; Lisa A. McKay; Kathleen Belanger; Brian P. Leaderer; Theodore R. Holford (5156-5164).
An integrated exposure model was developed that estimates nitrogen dioxide (NO2) 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 NO2 taken outside of 985 residences in Connecticut were used to develop the model. A second set of 120 outdoor NO2 measurements as well as cross-validation were used to validate the model. The model suggests that approximately 67% of the variation in NO2 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.
Keywords: Traffic-related air pollution; Exposure modeling; Outdoor nitrogen dioxide; Traffic volume; Land use;

Contribution of transition metals in the reactive oxygen species activity of PM emissions from retrofitted heavy-duty vehicles by Vishal Verma; Martin M. Shafer; James J. Schauer; Constantinos Sioutas (5165-5173).
We assessed the contribution of water-soluble transition metals to the reactive oxygen species (ROS) activity of diesel exhaust particles (DEPs) from four heavy-duty vehicles in five retrofitted configurations (V-SCRT, Z-SCRT, DPX, hybrid, and school bus). A heavy-duty truck without any control device served as the baseline vehicle. Particles were collected from all vehicle-configurations on a chassis dynamometer under three driving conditions: cruise (80 km h−1), transient UDDS, and idle. A sensitive macrophage-based in vitro assay was used to determine the ROS activity of collected particles. The contribution of water-soluble transition metals in the measured activity was quantified by their removal using a Chelex® complexation method. The study demonstrates that despite an increase in the intrinsic ROS activity (per mass basis) of exhaust PM with use of most control technologies, the overall ROS activity (expressed per km or per h) was substantially reduced for retrofitted configurations compared to the baseline vehicle. Chelex treatment of DEPs water extracts removed a substantial (≥70%) and fairly consistent fraction of the ROS activity, which ascertains the dominant role of water-soluble metals in PM-induced cellular oxidative stress. However, relatively lower removal of the activity in few vehicle-configurations (V-SCRT, DPX and school bus idle), despite a large aggregate metals removal, indicated that not all species were associated with the measured activity. A univariate regression analysis identified several transition metals (Fe, Cr, Co and Mn) as significantly correlated (R > 0.60; p < 0.05) with the ROS activity. Multivariate linear regression model incorporating Fe, Cr and Co explained 90% of variability in ROS levels, with Fe accounting for the highest (84%) fraction of the variance.
Keywords: Reactive oxygen species (ROS); Transition metals; Chelation; Diesel exhaust particles (DEPs);

Determinants of exposure to fine particulate matter (PM2.5) for waiting passengers at bus stops by Daniel Baldwin Hess; Paul David Ray; Anne E. Stinson; JiYoung Park (5174-5182).
This research evaluates commuter exposure to particulate matter during pre-journey commute segments for passengers waiting at bus stops by investigating 840 min of simultaneous exposure levels, both inside and outside seven bus shelters in Buffalo, New York. A multivariate regression model is used to estimate the relation between exposure to particulate matter (PM2.5 measured in μg m−3) and three vectors of determinants: time and location, physical setting and placement, and environmental factors. Four determinants have a statistically significant effect on particulate matter: time of day, passengers’ waiting location, land use near the bus shelter, and the presence of cigarette smoking at the bus shelter. Model results suggest that exposure to PM2.5 inside a bus shelter is 2.63 μg m−3 (or 18 percent) higher than exposure outside a bus shelter, perhaps due in part to the presence of cigarette smoking. Morning exposure levels are 6.51 μg m−3 (or 52 percent) higher than afternoon levels. Placement of bus stops can affect exposure to particulate matter for those waiting inside and outside of shelters: air samples at bus shelters located in building canyons have higher particulate matter than bus shelters located near open space.
Keywords: Particulate matter; Exposure; Pollution; Air quality; Bus shelters; Built environment; Second-hand smoke;

Air pollution characteristics associated with mesoscale atmospheric patterns in northwest continental Europe by Saskia Buchholz; Jürgen Junk; Andreas Krein; Günther Heinemann; Lucien Hoffmann (5183-5190).
An impact related daily air quality index (DAQx), calculated for 15 air quality monitoring stations (traffic, background, and industry) in Belgium, France, Germany and Luxembourg, was compared to mesoscale atmospheric patterns between 2001 and 2007. Meteorological conditions were described by the Hess and Brezowsky synoptic weather classification system and gridded data of the EU FP6 ENSEMBLES project of total precipitation and mean surface temperature. DAQx values indicate sufficient to poor air quality in the urban area of Brussels and at urban traffic stations, as well as satisfactory air quality at the background stations. The air quality index refers to more than 90% to the presence of high PM10, O3 and NO2 concentrations. SO2 and CO play only a minor role. The investigation of weather regimes indicates that zonal and mixed cyclonic circulation regimes are associated with better air quality than meridional and anticyclonic weather regimes. In general, weather regimes with high daily precipitation lead to better air quality than dryer air masses because of lower contribution of PM10 to the air quality index. A trend analysis of weather regimes from 1978 to 2007 shows significant (α  = 0.05) positive trends for weather classes associated with lower PM10 concentrations. The results of a case study at a German station examining the relationship between PM10 concentrations and local meteorological quantities (wind speed and precipitation) confirm the results of the regional analysis.
Keywords: Daily air quality index DAQx; Synoptic weather patterns; Trend analysis; Particulate matter PM10; Public health;

Physical characterization of aerosol particles during the Chinese New Year’s firework events by Min Zhang; Xuemei Wang; Jianmin Chen; Tiantao Cheng; Tao Wang; Xin Yang; Youguo Gong; Fuhai Geng; Changhong Chen (5191-5198).
Measurements for particles 10 nm to 10 μm were taken using a Wide-range Particle Spectrometer during the Chinese New Year (CNY) celebrations in 2009 in Shanghai, China. These celebrations provided an opportunity to study the number concentration and size distribution of particles in an especial atmospheric pollution situation due to firework displays. The firework activities had a clear contribution to the number concentration of small accumulation mode particles (100–500 nm) and PM1 mass concentration, with a maximum total number concentration of 3.8 × 104  cm−3. A clear shift of particles from nucleation and Aitken mode to small accumulation mode was observed at the peak of the CNY firework event, which can be explained by reduced atmospheric lifetimes of smaller particles via the concept of the coagulation sink. High particle density (2.7 g cm−3) was identified as being particularly characteristic of the firework aerosols. Recalculated fine particles PM1 exhibited on average above 150 μg m−3 for more than 12 hours, which was a health risk to susceptible individuals. Integral physical parameters of firework aerosols were calculated for understanding their physical properties and further model simulation.
Keywords: Fireworks; Number concentration; Size distribution; Coagulation sink; Particle density; Shanghai;

In this analysis, we characterize urban and rural ozone (O3) trends across the US for the periods 1980–2008 (29 years) and 1994–2008 (15 years) using three exposure metrics, which summarize daily O3 concentrations to reflect different ways O3 may affect human health and vegetation. We observe that a statistically significant trend at a specific monitoring site, using one exposure metric, does not necessarily result in a similar trend using the other two metrics. The two most common trends among the monitoring sites are either a continuation of negative trending over the 29-year period or a shift from negative to no trend status, indicating a leveling off of the trending. Very few sites exhibit statistically significant increases in the exposure indices. In characterizing the statistically significant changes in the distribution of hourly average O3, we observe subtle statistically significant changes in the lower part of the distribution (i.e., below 50 ppb) that are not necessarily captured by the trending patterns associated with the three exposure metrics. Using multisite data from 12 metropolitan cities, we find that as the frequency of higher hourly average concentrations is reduced, the lower hourly average concentrations also move upward toward the mid-level values. The change in the number of the hourly average concentrations in the lower range is consistent with decreased NO scavenging. We recommend assessing possible subtle shifts in O3 concentrations by characterizing changes in the distribution of hourly average concentrations by month. Identifying statistically significant monthly changes in the mid- and low-level hourly average concentrations may provide important information for assessing changes in physical processes associated with global climate change, long-range transport, and the efficacy of models used for emission and risk reductions. Our results indicate that it is important to investigate the change in the trending pattern with time (e.g., moving 15-year trending) in order to assess how year-to-year variability may influence the trend calculation.
Keywords: Monthly time trends; Surface ozone trends; Tropospheric ozone;

Environmental copper: Behaviour when involved in physical adsorption at several interfaces by Aziz Azri; Galal Elmanfe; René Olier; Mireille Privat (5211-5217).
From a literature-based assessment of the current knowledge about both the toxic or salutary properties of copper, this study focused on the determination, at 25 °C, of the interfacial properties of CuCl2, either alone or in mixture with carbofuran used, here, as a model of organics and/or pesticide. The interfaces under study were: i) the air/solution interface and ii) the silica/solution interface. The former is considered as a path for volatilization, whereas the latter permits a modelling of physical adsorption upon solids, which is the first and unavoidable step in any adsorption process. One should note that it can also mimic adsorption on some sandy soils. Coadsorption was clearly identified as implicated in an enhancement of the surface content of both solutes at both interfaces. However, at the two interfaces under study, the way the surface became structured led to opposite adsorption mechanisms for the organic compounds and the salt. A rough theory about ionic adsorption is also proposed.
Keywords: Copper dichloride; Carbofuran; Coadsorption; Environmental scattering;

SOA from methylglyoxal in clouds and wet aerosols: Measurement and prediction of key products by Yi Tan; Annmarie G. Carlton; Sybil P. Seitzinger; Barbara J. Turpin (5218-5226).
Aqueous OH radical oxidation of methylglyoxal in clouds and wet aerosols is a potentially important global and regional source of secondary organic aerosol (SOA). We quantify organic acid products of the aqueous reaction of methylglyoxal (30–3000 μM) and OH radical (approx. 4 × 10−12  M), model their formation in the reaction vessel and investigate how the starting concentrations of precursors and the presence of acidic sulfate (0–840 μM) affect product formation. Predicted products were observed. The predicted temporal evolution of oxalic acid, pyruvic acid and total organic carbon matched observations at cloud relevant concentrations (30 μM), validating this methylglyoxal cloud chemistry, which is currently being implemented in some atmospheric models of SOA formation. The addition of sulfuric acid at cloud relevant concentrations had little effect on oxalic acid yields. At higher concentrations (3000 μM), predictions deviate from observations. Larger carboxylic acids (≥C4) and other high molecular weight products become increasingly important as concentration increases, suggesting that small carboxylic acids are the major products in clouds while larger carboxylic acids and oligomers are important products in wet aerosols.
Keywords: Secondary organic aerosol (SOA); Isoprene; Methylglyoxal; Mutiphase photochemistry; Aqueous radical chemistry;

Airborne in-situ measurements were analyzed to investigate the effects of biomass burning and regional background aerosols on cloud condensation nuclei (CCN) activity in the Pacific Dust Experiment (PACDEX) during April and May 2007. Airmass trajectories with both horizontal and vertical motions were provided to identify the aerosol sources. In the biomass burning cases, the elevated aerosol layers were clearly observed at dry conditions because of the convection of airmass in the source region. The relative aging of aerosols was supported by the ratios of BC to particles with size ranging from 0.1 to 1.0 μm (N0.1–1.0) and BC to carbon monoxide. Compared to aerosols in the precedent plume of biomass burning, aged particles in the latter plume were more activated to CCN at 0.4% (CCN0.4%) than 0.1% supersaturation (CCN0.1%) due to aerosols chemical modification during the aging process. On the other hand, significant difference of CCN0.4% and CCN0.1% at regional background aerosols over the Pacific Ocean was due to the activated particles below 1 μm in diameter. Although higher concentrations of aged particles were observed over the eastern Pacific Ocean, activated aerosols to cloud droplet was comparatively similar in the western Pacific Ocean because of the similar concentrations of N0.1–1.0 in both cases.
Keywords: CCN activation; Black carbon; Regional aerosols; Aging; East Asia; PACDEX;

Emission factors and particulate matter size distribution of polycyclic aromatic hydrocarbons from residential coal combustions in rural Northern China by Guofeng Shen; Wei Wang; Yifeng Yang; Chen Zhu; Yujia Min; Miao Xue; Junnan Ding; Wei Li; Bin Wang; Huizhong Shen; Rong Wang; Xilong Wang; Shu Tao (5237-5243).
Coal consumption is one important contributor to energy production, and is regarded as one of the most important sources of air pollutants that have considerable impacts on human health and climate change. Emissions of polycyclic aromatic hydrocarbons (PAHs) from coal combustion were studied in a typical stove. Emission factors (EFs) of 16 EPA priority PAHs from tested coals ranged from 6.25 ± 1.16 mg kg−1 (anthracite) to 253 ± 170 mg kg−1 (bituminous), with NAP and PHE dominated in gaseous and particulate phases, respectively. Size distributions of particulate phase PAHs from tested coals showed that they were mostly associated with particulate matter (PM) with size either between 0.7 and 2.1 μm or less than 0.4 μm (PM0.4). In the latter category, not only were more PAHs present in PM0.4, but also contained higher fractions of high molecular weight PAHs. Generally, there were more than 89% of total particulate phase PAHs associated with PM2.5. Gas-particle partitioning of freshly emitted PAHs from residential coal combustions were thought to be mainly controlled by absorption rather than adsorption, which is similar to those from other sources. Besides, the influence of fuel properties and combustion conditions was further investigated by using stepwise regression analysis, which indicated that almost 57 ± 10% of total variations in PAH EFs can be accounted for by moisture and volatile matter content of coal in residential combustion.
Keywords: PAHs; Residential coal combustion; Emission factors; Size distribution;

This study provides the first comprehensive report on mass concentrations of particulate matter of various sizes, inorganic and organic gas concentrations monitored at three sampling sites in the city of Palermo (Sicily, Italy). It also provides information on the water-soluble species and trace elements. A total of 2054 PM10 (1333) and PM2.5 (721) daily measurements were collected from November 2006 to February 2008. The highest mass concentrations were observed at the urban stations, average values being about two times higher than those at the suburban (control) site. Time variations in PM10 and also PM10–2.5 were observed at the urban stations, the highest concentrations being measured in autumn and winter. CO, NOx, NO2, benzene, toluene and o-xylene concentrations peaked in autumn and winter, a pattern similar to those recorded for PM10 and PM10–2.5 mass levels, indicating the importance of traffic emissions in urban air pollution. 91% and 51% of the benzene measurements exceeded the limit of 5 μg m−3 at the two urban monitoring sites. Trace elements (As, Ba, Cr, Cu, Mo, Pb, Sb) suspected of being introduced into the atmosphere mainly by anthropogenic activities, were highly enriched with respect to local soil. Results indicate that a large fraction of PM10 (31–47% in weight) and PM2.5 (29% in weight) is made up of water-soluble ions. Ammonium sulphate and nitrate particles accounted for 14–29 wt% of particulate matter mass concentrations. Crustal and marine components, combined, account for 41% and 49% in PM2.5 and PM10, respectively. The calculated deficits in Cl- and NH4 + ions suggest that a proportion of these ions are lost, via the formation of gaseous NH4Cl or HCl and NH3.
Keywords: Air pollution; PM10 and PM2.5; Secondary airborne particulate; BTX; Trace elements;

This study presents, for the first time, long-term data of sub-μm particle number size distributions in the particle size range of 14–670 nm in the Mediterranean area of Rome. Data are analysed in terms of possible aerosol populations.A particular “event” including also measurements of nitrous acid mixing ratios in the atmosphere is further analysed. High statistical correlations are established: At daytime, between the unknown HONO formation rate and the product of NO2, J NO 2 , relative humidity, and sub-μm particle surface area concentration. At nighttime, between the volume concentration of the small Aitken mode particles and the HONO mixing ratios.The study would provide information on fine and ultrafine aerosol particle size distribution down to 14 nm in the Mediterranean suburban area of Rome. Besides, it would support previous works which have already provided several evidences for the existence of relations between the sub-μm aerosol populations and HONO. Our conclusions include speculations on possible daytime HONO formation mechanisms on particle surfaces in the accumulation mode size range, and nighttime mass formation mechanisms in common for the small Aitken mode particles and HONO.
Keywords: Ultrafine particles; Aerosol populations; HONO; Mediterranean;

Size-resolved aerosol chemical composition over the Italian Peninsula during typical summer and winter conditions by C. Carbone; S. Decesari; M. Mircea; L. Giulianelli; E. Finessi; M. Rinaldi; S. Fuzzi; A. Marinoni; R. Duchi; C. Perrino; T. Sargolini; M. Vardè; F. Sprovieri; G.P. Gobbi; F. Angelini; M.C. Facchini (5269-5278).
In the frame of the MIUR-AEROCLOUDS project (Study of Direct and Indirect Aerosol Effects on Climate), night-time and daytime size-segregated aerosol samples were collected concurrently at five different sites (near-city, urban, rural, marine and mountain background sites). The paper reports on the daily evolution of the main aerosol chemical characteristics as a function of particle size in different environments over the Italian Peninsula, spanning from the Po Valley to the south Tyrrhenian coast.Two 4-day intensive observation periods (IOPs) were undertaken in July 2007 and February 2008, under meteorological conditions typical of the summer and winter climate for Italy.In the summer IOP, under stable atmospheric conditions, at the low-altitude continental sites the diurnal evolution of the planetary boundary layer (PBL), induces an atmospheric dilution effect driving the particulate matter (PM) concentrations, while, at the mountain site, it determines the upward motion of polluted air masses from the Po Valley PBL in daytime.The fine fraction was dominated by ammonium salts and carbonaceous matter (water-soluble organic matter, WSOM, and water-insoluble carbonaceous matter, WINCM). High concentrations of ammonium sulphate and WSOM due to enhanced photochemical activity constituted the background aerosol composition over the whole country, whereas, ammonium nitrate and WINCM were more associated to local emissions (e.g. urban site with concentrations peaking in the finest size range due to strong local traffic-related sources of ultrafine particles).During the winter IOP in the Po Valley, the shallow PBL depths and low wind velocity, especially at night, favoured the condensation of semi-volatile species (i.e. organic matter and ammonium nitrate), causing the high fine PM concentration observed at ground level.
Keywords: Size-segregated; Aerosol; Chemical composition; Italy; Po valley;

Atmospheric flux of agricultural fumigants from raised-bed, plastic-mulch crop production systems by Dan O. Chellemi; Husein A. Ajwa; David A. Sullivan (5279-5286).
Atmospheric emission of methyl isothiocyanate (MITC), chloropicrin (CP), 1,3-dichloropropene (1,3-D), and dimethyl disulfide (DMDS) were measured in the field under fumigant application scenarios representative of raised bed–plastic-mulched crop production systems. For three fumigation sites located in Florida, cumulative emissions of 1,3-D, MITC and CP were less than 11%, 6% and 2%, respectively. For three fumigation sites in located in Georgia, cumulative emissions of MITC and CP were <13% and 12%, respectively while DMDS emissions varied from 37% to 95%. In the Florida sites, emission peak flux of CP occurred within the first 6 h after application. Peak emission of 1,3-D and MITC occurred between 100 and 144 h after application. In the Georgia sites where fumigated soil was covered by low density polyethylene (LDPE) plastic, emission peak flux of DMDS and MITC occurred between 12and 48 h after application. Key factors affecting atmospheric emissions were soil moisture, soil tilth and the resistance to fumigant diffusion of the plastic film used to cover soil following application. This study demonstrated reduced atmospheric emissions of agricultural fumigants under commercial production conditions when applied using good agricultural practices including soil water contents above field capacity, uniform soil tilth in the fumigation zone and the use of metalized or virtually impermeable films to further reduce fumigant emissions. The results of this study show a need for regional flux studies due to the various interactions of soil and climate with local agricultural land management practices.
Keywords: Low density polyethylene; Virtually impermeable film; Methyl isothiocyanate; Dimethyl disulfide; 1,3-Dichloropropene; Chloropicrin;

Remote sampling of a CO2 point source in an urban setting by Nathan Sparks; Ralf Toumi (5287-5294).
High frequency CO2 and wind speed measurements were used to examine the urban baseline eddy covariance CO2 flux and analyse the CO2 rich plume from a local power station. A reliable relationship between high frequency CO2 maxima and the rate of CO2 emission at the power station was established. This relationship was shown to be highly dependant on wind speed. The ensemble mean plume was found to be Gaussian in horizontal profile with a width dependant on wind speed. The relationship between peak CO2 mixing ratio and averaging time was shown to be a simple power law with a time exponent of approximately 0.5. The large, short pulses in CO2 mixing ratio in the power plant plume were found to have an approximately Lorentzian shape. These pulses generated negative vertical eddy flux measurements so data from the plume sector were necessarily excluded from the flux baseline results. The plume-excluded flux had a similar magnitude and variability to those reported in other urban CO2 flux studies despite this site not being ideal due to the proximity of roughness elements to the measurement point.
Keywords: Emissions monitoring; Plume; Eddy covariance; Averaging time; Pulse;

The radiative impact of aerosols is one of the largest sources of uncertainty in estimating anthropogenic climate perturbations. Here we have used independent ground-based radiometer measurements made simultaneously with comprehensive measurements of aerosol microphysical and optical properties at a highly populated urban site, Bangalore (13.02°N, 77.6°E) in southern India during a dedicated campaign during winter of 2004 and summer and pre-monsoon season of 2005. We have also used longer term measurements carried out at this site to present general features of aerosols over this region. The aerosol radiative impact assessments were made from direct measurements of ground reaching irradiance as well as by incorporating measured aerosol properties into a radiative transfer model. Large discrepancies were observed between measured and modeled (using radiative transfer models, which employed measured aerosol properties) radiative impacts. It appears that the presence of elevated aerosol layers and (or) inappropriate description of aerosol state of mixing are (is) responsible for the discrepancies. On a monthly scale reduction of surface irradiance due to the presence of aerosols (estimated using radiative flux measurements) varies from 30 to 65 W m−2. The lowest values in surface radiative impact were observed during June when there is large reduction in aerosol as a consequence of monsoon rainfall. Large increase in aerosol-induced surface radiative impact was observed from winter to summer. Our investigations re-iterate the inadequacy of aerosol measurements at the surface alone and importance of representing column properties (using vertical profiles) accurately in order to assess aerosol-induced climate changes accurately.
Keywords: Aerosols; Radiative fluxes; Climate change; Radiative forcing; Radiation budget;

Seasonal ozone behavior along an elevation gradient in the Colorado Front Range Mountains by Molly Brodin; Detlev Helmig; Samuel Oltmans (5305-5315).
Ambient surface ozone was monitored for one year at a series of seven sites along an elevation gradient from 1600 m to 3500 m above sea level (ASL) in Boulder County, Colorado. Spatial variability of ozone, quantified as the root mean squared deviation of hourly ozone per kilometer horizontal separation, decreased with elevation and distance from local sources, validating the assumption that (except at the City of Boulder (BO) site) the results of the study are representative of the Colorado Front Range. The northern hemisphere (NH) tropospheric spring ozone peak was clearly apparent in late April and early May and affected ozone at all elevations. Ozone consistently increased with elevation during winter, with a mean monthly rate of 1.5 ppbv per 100 m elevation. In summer, this monotonic increase in ozone with elevation was not observed; instead mean monthly ozone increased in two steps, by ∼15 ppbv between 1610 m and 1940 m ASL and by ∼10 ppbv between 3350 m and 3530 m ASL to a maximum of 60 ppbv. The amplitude of the diurnal ozone cycle decreased with increasing elevation. Average summertime diurnal swings in ozone concentration had a magnitude of 29 ppbv at 1610 m ASL, and 7–16 ppbv at the mid-elevation sites. In winter a diurnal cycle was observed only at the BO site, ozone concentrations at the remaining six locations changed on a multi-day timescale, indicating regional background behavior as the primary factor for wintertime ozone. Even the highest elevation site was influenced by transported urban air pollution in summer, indicated by the average 5 ppbv diurnal increase in ozone. Ozone exposure at the mid- to high-elevation sites in many instances approached and exceeded the 8-h National Ambient Air Quality Standard of 75 ppbv. The elevated ozone levels along this transect were interpreted to be caused by the confounding effects of the high elevation of these sites, increased ozone in long-range transported air, and anthropogenic ozone production in air transported from the nearby urban and suburban areas east of the Colorado Front Range Mountains.
Keywords: Surface ozone; Elevation profile;

Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography by Kimitaka Kawamura; Leonard A. Barrie; Desiree Toom-Sauntry (5316-5319).
Oxalate, the anion of oxalic acid, is one of the most abundant measurable organic species in atmospheric aerosols. Traditionally, this bifunctional species has been measured by gas chromatography (GC) after derivatization to butyl ester and by ion chromatography (IC) without derivatization. However, there are few published comparisons of the two techniques. Here, we report the results of an intercomparison study for the measurement of oxalic acid in Arctic aerosols (<2.5 μm, n = 82) collected in 1992 using GC and IC. The concentrations of oxalic acid by GC ranged from 6.5–59.1 ng m−3 (av. 26.0 ng m−3, median 26.2 ng m−3) whereas those by IC ranged from 6.6–52.1 ng m−3 (av. 26.6 ng m−3, median 25.4 ng m−3). They showed a good correlation (r = 0.84) with a slope of 0.96. Thus, observations of oxalate obtained by GC employing dibutyl esters are almost equal to those by IC. Because the accuracy of oxalic acid by GC method largely depends on the method used, it is important to strictly examine the recovery in each study.
Keywords: Oxalic acid; Gas chromatography; Oxalate; Ion chromatography; Aerosols;