Atmospheric Environment (v.43, #32)

Comparison of particle emissions from small heavy fuel oil and wood-fired boilers by Olli Sippula; Jouni Hokkinen; Harri Puustinen; Pasi Yli-Pirilä; Jorma Jokiniemi (4855-4864).
Flue gas emissions of wood and heavy fuel oil (HFO) fired district heating units of size range 4–15 MW were studied. The emission measurements included analyses of particle mass, number and size distributions, particle chemical compositions and gaseous emissions. Thermodynamic equilibrium calculations were carried out to interpret the experimental findings.In wood combustion, PM1 (fine particle emission) was mainly formed of K, S and Cl, released from the fuel. In addition PM1 contained small amounts of organic material, CO3, Na and different metals of which Zn was the most abundant. The fine particles from HFO combustion contained varying transient metals and Na that originate from the fuel, sulphuric acid, elemental carbon (soot) and organic material. The majority of particles were formed at high temperature (>800 °C) from V, Ni, Fe and Na. At the flue gas dew point (125 °C in undiluted flue gas) sulphuric acid condensed forming a liquid layer on the particles. This increases the PM1 substantially and may lead to partial dissolution of the metallic cores.Wood-fired grate boilers had 6–21-fold PM1 and 2–23-fold total suspended particle (TSP) concentrations upstream of the particle filters when compared to those of HFO-fired boilers. However, the use of single field electrostatic precipitators (ESP) in wood-fired grate boilers decreased particle emissions to same level or even lower as in HFO combustion. On the other hand, particles released from the HFO boilers were clearly smaller and higher in number concentration than those of wood boilers with ESPs. In addition, in contrast to wood combustion, HFO boilers produce notable SO2 emissions that contribute to secondary particle formation in the atmosphere. Due to vast differences in concentrations of gaseous and particle emissions and in the physical and chemical properties of the particles, HFO and wood fuel based energy production units are likely to have very different effects on health and climate.
Keywords: Residual fuel oil; Biomass; Combustion; Fine particles; Aerosol; Particle emissions;

Experiments were carried out on a diesel engine operating on Euro V diesel fuel, pure biodiesel and biodiesel blended with methanol. The blended fuels contain 5%, 10% and 15% by volume of methanol. Experiments were conducted under five engine loads at a steady speed of 1800 rev min−1 to assess the performance and the emissions of the engine associated with the application of the different fuels. The results indicate an increase of brake specific fuel consumption and brake thermal efficiency when the diesel engine was operated with biodiesel and the blended fuels, compared with the diesel fuel. The blended fuels could lead to higher CO and HC emissions than biodiesel, higher CO emission but lower HC emission than the diesel fuel. There are simultaneous reductions of NOx and PM to a level below those of the diesel fuel. Regarding the unregulated emissions, compared with the diesel fuel, the blended fuels generate higher formaldehyde, acetaldehyde and unburned methanol emissions, lower 1,3-butadiene and benzene emissions, while the toluene and xylene emissions not significantly different.
Keywords: Biodiesel; Methanol; Regulated emissions; Unregulated emissions; Diesel engine;

On the influence of chemical initial and boundary conditions on annual regional air quality model simulations for North America by Mehrez Samaali; Michael D. Moran; Véronique S. Bouchet; Radenko Pavlovic; Sophie Cousineau; Mourad Sassi (4873-4885).
The influence of chemical initial conditions and chemical lateral boundary conditions (CLBCs) on long-term regional air quality model simulations was investigated using outputs from an annual simulation of the year 2002 on a North American domain. This simulation was carried out using the AURAMS regional air quality model. It was subdivided into three multi-month segments with two overlap periods (May 15–30 and September 1–30) to allow the segments to be run in parallel. For this approach to work, model predictions had to match very closely by the end of the two-week and four-week overlap periods. The time required for the values of daily domain-average surface PM2.5 concentration to match for the two simulation segments associated with each of the two overlap periods was four and six days, respectively. For individual locations within the model domain, however, the required spin-up period was as much as nine days, considerably longer than the 2–4-day spin-up period usually assumed in the literature. For ozone, on the other hand, the daily domain-average surface ozone concentration values did not converge for either overlap period. A zero-gradient CLBC had been used for all run segments and species. When a time-invariant CLBC for ozone was used instead, the daily domain-average surface ozone concentration values behaved more realistically and did converge after fewer than three days. A similar improvement was also obtained for individual locations, but with spin-up periods of up to nine days. Model chemical spin-up time thus seems to be dependent on the species considered, the time required for the influence of the inflow boundaries to reach all locations within the domain, and the impact of local emissions sources. These results suggest the use of a spin-up period of longer than one week for a large (continental) domain and long-term simulation of PM2.5 and O3 rather than the 2–4 days commonly assumed in the literature.
Keywords: Boundary condition; Initial condition; Spin-up; Ozone; Particulate matter;

Many of the products of the reaction of naphthalene (Naph) with the OH radical in a reaction chamber were identified. Previously unidentified products included 1,2-naphthoquinone (NQ), oxygenated indenes and benzopyrones. Possible pathways for the formation of 1,2-NQ and 1,4-NQ are proposed. In the chamber reactions, more 1,2-NQ than 1,4-NQ partitioned to the particle phase. From this result we infer that, in the atmosphere, the percentage of 1,2-NQ in the particle phase should be greater than that for the 1,4-NQ. Because both of these compounds are considered to be toxic, and since they appear in both the gas and particle phases in the reaction chamber, and by implication in the atmosphere, it is considered important that both the gas and particle phases of these two compounds should be measured to assess their impact on human health.
Keywords: Naphthalene; OH radical reaction; 1,2-Naphthoquinone; 1,4-Naphthoquinone; Gas to particle partitioning; Secondary organic aerosol (SOA);

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC by Luyi C. Ding; Fu Ke; Daniel K.W. Wang; Tom Dann; Claire C. Austin (4894-4902).
Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m−3), 16 PAHs (0.02–1.83 ng m−3), and biomarkers (0.02–0.18 ng m−3). Daily levels of these organics were 4.89–74.38 ng m−3, 0.27–100.24 ng m−3, 0.14–4.39 ng m−3, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.
Keywords: Direct thermal desorption; GC/MS; Organic speciation; PM2.5; OC/EC;

To investigate the chemical characteristics of precipitation in the polluted coastal atmosphere, a total of 46 event-based precipitation samples were collected using a wet-only automatic precipitation collector from September 2006 to October 2007 at metropolitan Newark, New Jersey in the US East Coast. Samples were analyzed by ion chromatography for the concentrations of major inorganic ions (Cl, NO3 , SO4 2−, F, NH4 +, Ca2+, Mg2+, Na+, K+) and organic acid species (CH3COO, HCOO, CH2(COO)2 2−, C2O4 2−). Selected trace metals (Sb, Pb, Al, V, Fe, Cr, Co, Ni, Cu, Zn, Cd) in samples were determined by ICPMS. Mass concentration results show that SO4 2− was the most dominant anion accounting for 51% of the total anions, controlling the acidity of the precipitation. NH4 + accounted for 48.6% of the total cations, dominating the precipitation neutralization. CH3COO and HCOO were the two dominant water-soluble organic acid species, accounting for 42% and 40% of the total organic acids analyzed, respectively. Al, Zn and Fe were the three major trace metals in precipitation, accounting for 34%, 27%, and 25% of the total mass of metals analyzed. The pH values in precipitation ranged from 4.4 to 4.9, indicating an acidic nature. Enrichment Factor (EF) Analysis showed that Na+, Cl, Mg2+ and K+ in the precipitation were primarily of marine origin, while most of the Fe, Co and Al were from crust sources. Pb, V, Cr, Ni were moderately enriched with EFs ranging 43–410, while Zn, Sb, Cu, Cd and F were highly enriched with EFs > 700, indicating significant anthropogenic influences. Factor analysis suggests 6 major sources contributing to the observed composition of precipitation at this location: (1) nitrogen-enriched soil, (2) secondary pollution processes, (3) marine sources, (4) incinerations, (5) oil combustions, and (6) malonate–vanadium enriched sources. To further explore the source–precipitation event relationships and seasonality, cluster analysis was performed for all precipitation events. Results show that about half of the precipitation events were characterized by mixed sources. Significant influences of nitrogen-enriched soil and marine sources were associated with precipitation events in spring and autumn, while secondary pollution processes, incineration and oil combustion contributed greatly in summer.
Keywords: Precipitation; Trace metals; Anions and cations; Urban; Enrichment factor; Factor analysis; Cluster analysis;

Simple, inexpensive and accurate methods for assessing the spatial distribution of traffic emissions are badly needed for the environmental management in South American cities. In this study, various spatial disaggregation methods of traffic emissions of carbon monoxide are presented and evaluated for a large city (Santiago de Chile). Previous methods have used a simplified road network as a proxy for deriving spatial patterns of emissions. However, these approaches resulted in underestimation of emissions in urban centers, industrial zones and highly loaded roads, as well as overestimation in residential zones. Here we modify these methods by adding data correlated with the emissions (e.g. traffic counts, vehicles mean speed, road capacity) solving partially or completely the indicated problems. After an accuracy-simplicity analysis two methodologies stand out over the others: using traffic count classification and using a land use map, both combined with a simplified road network. Both are top–down approaches that correlate well (∼0.9) with the reference emissions and capture emission peaks (within 30% relative error). Hence the proposed changes allow an improved balance between accuracy and costs (monetary, availability of data and time to obtain data).
Keywords: CO urban distribution; Hot exhaust emissions; Road vehicles pollution; Traffic activity data; Top–down methodologies; Santiago de Chile;

The effect of improved nowcasting of precipitation on air quality modeling by G.T. Geertsema; B.G.J. Wichers Schreur (4924-4934).
The predictive potential of air quality models and thus their value in emergency management and public health support are critically dependent on the quality of their meteorological inputs. The atmospheric flow is the primary cause of the dispersion of airborne substances. The scavenging of pollutants by cloud particles and precipitation is an important sink of atmospheric pollution and subsequently determines the spatial distribution of the deposition of pollutants. The long-standing problem of the spin-up of clouds and precipitation in numerical weather prediction models limits the accuracy of the prediction of short-range dispersion and deposition from local sources. The resulting errors in the atmospheric concentration of pollutants also affect the initial conditions for the calculation of the long-range transport of these pollutants. Customary the spin-up problem is avoided by only using NWP (Numerical Weather Prediction) forecasts with a lead time greater than the spin-up time of the model. Due to the increase of uncertainty with forecast range this reduces the quality of the associated forecasts of the atmospheric flow.In this article recent improvements through diabatic initialization in the spin-up of large-scale precipitation in the Hirlam NWP model are discussed. In a synthetic example using a puff dispersion model the effect is demonstrated of these improvements on the deposition and dispersion of pollutants with a high scavenging coefficient, such as sulphur, and a low scavenging coefficient, such as cesium-137. The analysis presented in this article leads to the conclusion that, at least for situations where large-scale precipitation dominates, the improved model has a limited spin-up so that its full forecast range can be used. The implication for dispersion modeling is that the improved model is particularly useful for short-range forecasts and the calculation of local deposition. The sensitivity of the hydrological processes to proper initialization implies that the spin-up problem may reoccur with changes in the model and increased model resolution. Spin-up should be an ongoing concern for atmospheric modelers.
Keywords: Relaxation process; Precipitation; Wet deposition; Emergency response; Air pollution; Mesoscale modeling; Dispersion modeling;

A precipitation dataset collected on a 0.5 mm precipitation basis was studied. The parameters analyzed in this study were the pH (i.e., H+ concentration), electric conductivity (EC), and S O 4 2− and N O 3 − concentrations. The  N O 3 − concentration clearly decayed with an increase of the precipitation amount, while a larger variation was observed in the S O 4 2− concentration even when the precipitation amount increased. Assuming that the decaying N O 3 − concentration (0.70 μg ml−1) was the result of the rainout process, the estimates were: annual total deposition, 3252 mg m−2 yr−1; rainout process, 1092 mg m−2 yr−1; and rainout/total, 34%. The estimates for S O 4 2− were: annual total deposition, 4687 mg m−2 yr−1; rainout process, 2096 mg m−2 yr−1; and rainout/total, 45%.
Keywords: Acid rain; Nitrate; Sulfate; Washout; Rainout;

Model reduction via principal component truncation for the optimal design of atmospheric monitoring networks by Olivier Saunier; Marc Bocquet; Anne Mathieu; Olivier Isnard (4940-4950).
A numerically efficient methodology for the optimal design of monitoring networks aiming at the surveillance of accidental atmospheric release is proposed in this paper. In a realistic context, the design of such a network requires the knowledge of a database of potential dispersion accidents occurring in the domain of the study. An objective function measures the ability of a potential network to provide measurements in order to reconstruct any accidental plume taken from the database. In the optimisation of such cost functions with respect to networks, most of the computational time is spent in the evaluation of the function, especially if the accidents database is large. In this paper we show how to optimally reduce this database and how this affects the design via a mathematical expansion in the cost function. We introduce methods based on principal component analysis, which are rigorous when the cost function is of least-squares type. These methods are then tested and validated with success on the design of a radionuclides monitoring network to be deployed over France. This is the so-called Descartes network which will be operated by the French Institute for Radiation and Nuclear Safety. These techniques are then applied on Descartes to solve several issues that are computationally demanding, but are also of more general interest, such as: how should one sequentially deploy the stations of the network? How is affected the optimal network when other European potential radiological sources are taken into account?
Keywords: Network design; Atmospheric dispersion; Principal component analysis; Model reduction; Radionuclides;

Sensitivity of a molecular marker based positive matrix factorization model to the number of receptor observations by YuanXun Zhang; Rebecca J. Sheesley; Min-Suk Bae; James J. Schauer (4951-4958).
To investigate the impact of the number of observations on molecular marker-based positive matrix factorization (MM-PMF) source apportionment models, daily PM2.5 samples were collected in East St. Louis, IL, from April 2002 through May 2003. The samples were analyzed for daily 24-h average concentrations of elemental and organic carbon, trace elements, and speciated particle-phase organic compounds. A total of 273 sets of observations were used in the model and consisted of all valid sets of observations from the year long data set minus one sixth of the measurements, which were collected every 6th day and were analyzed by different chemical analysis techniques. In addition to the base case of 273 samples, systematic subsets of the data set were analyzed by PMF. These subsets of data included 50% of the observations (135–138 days), 33% of the observations (90–92 days) and 20% of the observations (52–56 days). In addition, model runs were also examined that used 48-h, 72-h, 6-day, and weekly average concentrations as model inputs. All MM-PMF model runs were processed following the same procedures to explore the stability of the source attribution results. Consistent with previous MM-PMF results for East St. Louis, the main sources of organic aerosol were found to be mobile sources, secondary organic aerosols (SOAs), resuspended soil and biomass combustions, as well as an n-alkane dominated point source and other combustion sources. The MM-PMF model was reasonably stable when the number of observations in the input was reduced to ninety, or approximately 33% of observations present in the base case. In these cases, the key factors including resuspended soil, mobile and secondary factors, which accounted for more than 70% of the measured OC concentrations, were stable as defined by a relative standard deviation (RSD) of less than 30%. Similar results were obtained from the smaller data subsets, but resulted in larger uncertainties, with several of these factors yielding RSD of greater than 30%. The three factors with the largest OC contributions were more stable than the other minor factors, even when the number of observations was nominally 50 days. Secondary organic aerosol (SOA) was the most stable factor observed in the model runs. Since it is unclear if these results can be broadly applied to all MM-PMF models, additional studies of this nature are needed to assess the broader applicability of these conclusions. Until such studies are implemented, this paper provides a foundation to design future studies in sampling strategies for source apportionment using MM-PMF.
Keywords: Source attribution; Factor analysis; Organic aerosol;

The fine particle emissions from a U. S. certified non-catalytic wood stove and a zero-clearance fireplace burning Quercus rubra L. (northern red oak) and Pseudotsuga menziesii (Douglas fir) cordwood each at two different moisture levels were determined. Emission testing was performed using both time-integrated and continuous instrumentation for total particle mass, particle number, particle size distribution, and fixed combustion gases using an atmospheric wind tunnel, full-flow laboratory dilution tunnel, and dilution stack sampler with a comparison made between the three dilution systems and two sampling filter types. The total mass emission factors (EFs) for all dilution systems and filter media are extremely variable ranging from <1 to ∼55 g kg−1 of dry wood depending on the combination of appliance type, wood species and moisture content, filter medium, and dilution system. For Teflon filter sampling of stove emissions in the wind tunnel, the total mass EFs varied from ∼2 to 8 g kg−1 of dry fuel depending on wood type whereas the equivalent fireplace emissions burning wet oak averaged 11 g kg−1. A substantial number of ultrafine particles in the accumulation size range were also observed during all tests as determined by an Electrical Low Pressure Impactor (ELPI) and Scanning Mobility Particle Sizer. The PM-2.5 (particles ≤2.5 μm in aerodynamic diameter) fractions determined from the ELPI electrometer data ranged from 93 to 98% (mass) depending on appliance type as reported previously by .
Keywords: Wood burning appliances; Room heaters; Fireplaces; Particle emissions; Dilution systems;

Volcanic sulphate and arctic dust plumes over the North Atlantic Ocean by J. Ovadnevaite; D. Ceburnis; K. Plauskaite-Sukiene; R. Modini; R. Dupuy; I. Rimselyte; M. Ramonet; K. Kvietkus; Z. Ristovski; H. Berresheim; C.D. O'Dowd (4968-4974).
High time resolution aerosol mass spectrometry measurements were conducted during a field campaign at Mace Head Research Station, Ireland, in June 2007. Observations on one particular day of the campaign clearly indicated advection of aerosol from volcanoes and desert plains in Iceland which could be traced with NOAA Hysplit air mass back trajectories and satellite images. In conjunction with this event, elevated levels of sulphate and light absorbing particles were encountered at Mace Head. While sulphate concentration was continuously increasing, nitrate levels remained low indicating no significant contribution from anthropogenic pollutants. Sulphate concentration increased about 3.8 μg m−3 in comparison with the background conditions. Corresponding sulphur flux from volcanic emissions was estimated to about 0.3 TgS yr−1, suggesting that a large amount of sulphur released from Icelandic volcanoes may be distributed over distances larger than 1000 km. Overall, our results corroborate that transport of volcanogenic sulphate and dust particles can significantly change the chemical composition, size distribution, and optical properties of aerosol over the North Atlantic Ocean and should be considered accordingly by regional climate models.
Keywords: Volcanic sulphate aerosol; Icelandic dust; Particle acidity; Aerosol properties;

Spatial and temporal variations in traffic-related particulate matter at New York City high schools by Molini M. Patel; Steven N. Chillrud; Juan C. Correa; Marian Feinberg; Yair Hazi; K.C. Deepti; Swati Prakash; James M. Ross; Diane Levy; Patrick L. Kinney (4975-4981).
Relatively little is known about exposures to traffic-related particulate matter at schools located in dense urban areas. The purpose of this study was to examine the influences of diesel traffic proximity and intensity on ambient concentrations of fine particulate matter (PM2.5) and black carbon (BC), an indicator of diesel exhaust particles, at New York City (NYC) high schools. Outdoor PM2.5 and BC were monitored continuously for 4–6 weeks at each of 3 NYC schools and 1 suburban school located 40 km upwind of the city. Traffic count data were obtained using an automated traffic counter or video camera. BC concentrations were 2–3 fold higher at urban schools compared with the suburban school, and among the 3 urban schools, BC concentrations were higher at schools located adjacent to highways. PM2.5 concentrations were significantly higher at urban schools than at the suburban school, but concentrations did not vary significantly among urban schools. Both hourly average counts of trucks and buses and meteorological factors such as wind direction, wind speed, and humidity were significantly associated with hourly average ambient BC and PM2.5 concentrations in multivariate regression models. An increase of 443 trucks/buses per hour was associated with a 0.62 μg/m3 increase in hourly average BC at an NYC school located adjacent to a major interstate highway. Car traffic counts were not associated with BC. The results suggest that local diesel vehicle traffic may be important sources of airborne fine particles in dense urban areas and consequently may contribute to local variations in PM2.5 concentrations. In urban areas with higher levels of diesel traffic, local, neighborhood-scale monitoring of pollutants such as BC, which compared to PM2.5, is a more specific indicator of diesel exhaust particles, may more accurately represent population exposures.
Keywords: Diesel traffic; Particulate matter; Black carbon; Urban air pollution;

The objective of this study is to investigate the air ventilation impacts of the so called “wall effect” caused by the alignment of high-rise buildings in complex building clusters. The research method employs the numerical algorithm of computational fluid dynamics (CFD – FLUENT) to simulate the steady-state wind field in a typical Hong Kong urban setting and investigate pollutant dispersion inside the street canyon utilizing a pollutant transport model. The model settings of validation study were accomplished by comparing the simulation wind field around a single building block to wind tunnel data. The results revealed that our model simulation is fairly close to the wind tunnel measurements. In this paper, a typical dense building distribution in Hong Kong with 2 incident wind directions (0° and 22.5°) is studied. Two performance indicators are used to quantify the air ventilation impacts, namely the velocity ratio (VR) and the retention time (Tr ) of pollutants at the street level. The results indicated that the velocity ratio at 2 m above ground was reduced 40% and retention time of pollutants increased 80% inside the street canyon when high-rise buildings with 4 times height of the street canyon were aligned as a “wall” upstream. While this reduction of air ventilation was anticipated, the magnitude is significant and this result clearly has important implications for building and urban planning.
Keywords: Air ventilation; Wall effect; Retention time; Velocity ratio; Pollutant dispersion; Urban air quality;

High methane emissions from a littoral zone on the Qinghai-Tibetan Plateau by Huai Chen; Ning Wu; Shouping Yao; Yongheng Gao; Dan Zhu; Yanfen Wang; Wan Xiong; Xingzhong Yuan (4995-5000).
The littoral zones of lakes have been regarded as hotspots of methane (CH4) fluxes through several studies. In the present study, we measured CH4 fluxes in six kinds of littoral zones of Huahu Lake on the Qinghai-Tibetan Plateau in the peak growing season of 2006 and 2007. We found that CH4 efflux (ranging from −0.1 to 90 mg CH4 m−2 h−1) from the littoral zones of this lake was relatively high among those of boreal and temperate lakes. Our results also showed that emergent plant zones (Hippuris vulgaris and Glyceria maxima stands) recorded the highest CH4 flux rate. The CH4 flux in the floating mat zone of Carex muliensis was significantly lower than those of the emergent plant zones. CH4 fluxes in the floating-leaved zone of Polygonum amphibium and bare lakeshore showed no significant difference and ranked last but one, only higher than that of the littoral meadow (Kobresia tibetica). Plant biomass and standing water depths were important factors to explain such spatial variations in CH4 fluxes. No significant temporal variations in CH4 fluxes were found due to the insignificant variations of physical factors in the peak growing season. These results may help in our understanding of the importance of the littoral zone of lakes, especially the emergent plant zone, as a hotspot of CH4 emission.
Keywords: Zoige plateau; Greenhouse gases fluxes; Alpine wetland; Qinghai-Tibetan Plateau; Littoral wetlands; Methane budget;

The interaction of N2O5 with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO3) and quartz (SiO2) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10−3 for CaCO3, (8.6 ± 0.6) × 10−3 for Quartz and (9.8 ± 1.0) × 10−3 for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.
Keywords: Mineral dust; Heterogeneous; Nitrogen oxides; Dinitrogen pentoxide; Troposphere;

Weighted road density: A simple way of assigning traffic-related air pollution exposure by Nectarios Rose; Christine Cowie; Robert Gillett; Guy B. Marks (5009-5014).
Existing traffic variables used for predicting NO2 in epidemiological studies are either difficult to acquire or explain only a small proportion of the variance. The purpose of this study was to develop and validate a new predictor, weighted road density, which combines the maximum amount of information related to traffic into a single variable without the requirement of obtaining traffic counts for a given area.Two week NO2 samples were collected using the readings of up to 32 passive samplers on 3 separate rounds between September and December 2006 and again in 2007. Several types of traffic related explanatory variables based on traffic counts, distance to main road and the proposed weighted road density were constructed using GIS software, and tested for association with the NO2 samplers. Assessment of the best model was based on R 2 values, as well as leave-one-out cross validation.The weighted road density variable and the density variable based on traffic counts resulted in a similar R 2 (0.59) for predicting NO2, although weighted road density was much easier to construct and outperformed other variables such as distance to main road.As well as being a powerful predictor for use in a land use regression model, weighted road density can be used as a proxy for exposure to traffic-related pollution, for use in circumstances where direct measurements of pollutant levels are not feasible or are not required.
Keywords: Air pollution; Exposure assessment; Road traffic; Land use regression; Geographic information systems;

The use of regulatory and compliance-based modeling for air quality impact assessment is invariably relied upon to predict future air quality under various management scenarios particularly where air quality monitoring data are limited. This paper examines the dispersion from a multi-stack cement manufacturing complex with associated quarries and transport activities for regulatory compliance under uncertain emission and meteorological conditions. The concentrations of CO, NOx, SO2 and PM at sensitive receptor locations were used as indicators in comparison to World Health Organization (WHO) interim guidelines. Exceedance exposure areas were delineated under bounded uncertainties in input emission factors and meteorological parameters. Planning and management initiatives were tested to control/minimize potential exposure. Compared to the case of low emissions and actual meteorological conditions, the consideration of worst emissions coupled to worst meteorological conditions enlarged the boundaries of the exceedance exposure areas considerably. The implementation of best available technologies and enforcement of emission standards improved air quality in the region significantly and lowered the exposure at many population centers to below health standards. Uncertainty in the output of atmospheric dispersion models continues to play a significant role to be considered at the point where science is translated into political decision making.
Keywords: Cement emissions; Air quality impact assessment; Air quality management; Chekka; Lebanon;

A field study of factors influencing the concentrations of a traffic-related pollutant in the vicinity of a complex urban junction by A.S. Tomlin; R.J. Smalley; J.E. Tate; J.F. Barlow; S.E. Belcher; S.J. Arnold; A. Dobre; A. Robins (5027-5037).
The paper describes a field study focused on the dispersion of a traffic-related pollutant within an area close to a busy intersection between two street canyons in Central London. Simultaneous measurements of airflow, traffic flow and carbon monoxide concentrations ([CO]) are used to explore the causes of spatial variability in [CO] over a full range of background wind directions. Depending on the roof-top wind direction, evidence of both flow channelling and recirculation regimes were identified from data collected within the main canyon and the intersection. However, at the intersection, the merging of channelled flows from the canyons increased the flow complexity and turbulence intensity. These features, coupled with the close proximity of nearby queuing traffic in several directions, led to the highest overall time-average measured [CO] occurring at the intersection. Within the main street canyon, the data supported the presence of a helical flow regime for oblique roof-top flows, leading to increased [CO] on the canyon leeward side. Predominant wind directions led to some locations having significantly higher diurnal average [CO] due to being mostly on the canyon leeward side during the study period. For all locations, small changes in the background wind direction could cause large changes in the in-street mean wind angle and local turbulence intensity, implying that dispersion mechanisms would be highly sensitive to small changes in above roof flows. During peak traffic flow periods, concentrations within parallel side streets were approximately four times lower than within the main canyon and intersection which has implications for controlling personal exposure. Overall, the results illustrate that pollutant concentrations can be highly spatially variable over even short distances within complex urban geometries, and that synoptic wind patterns, traffic queue location and building topologies all play a role in determining where pollutant hot spots occur.
Keywords: Dispersion; Intersection; Street canyon; Traffic pollution; Turbulence; DAPPLE field campaign;

Modification of cloud condensation nucleus activity of organic aerosols by hydroxyl radical heterogeneous oxidation by I.J. George; R.Y.-W. Chang; V. Danov; A. Vlasenko; J.P.D. Abbatt (5038-5045).
The modification of cloud condensation nucleus (CCN) activity of saturated organic particles resulting from heterogeneous oxidation by OH radicals was studied. Submicron Bis-2-ethylhexyl sebacate (BES) and stearic acid particles were exposed to OH radicals in a reactor flow tube and CCN activity was monitored. The hygroscopicity parameter, κ, for monodisperse stearic acid and BES particles of 145–150 nm in size increased from <0.008 up to 0.08 as a result of OH exposures equivalent to atmospheric exposure timescales of several days to a week. The oxidation of stearic acid particles led to a 50% reduction in particle volume at high OH exposures, indicating an enhanced degree of volatilization of oxidation products compared to oxidized BES particles, along with possible shape/phase change. Surface tension measurements of water extracts of oxidized BES films showed a significant reduction in surface tension due to oxidation. Köhler calculations modeling the CCN measurements suggest that the surface active oxidation products play an important role.
Keywords: OH; CCN; Chemical aging; Surface tension;

Regional NOx emission inversion through a four-dimensional variational approach using SCIAMACHY tropospheric NO2 column observations by Tianfeng Chai; Gregory R. Carmichael; Youhua Tang; Adrian Sandu; Andreas Heckel; Andreas Richter; John P. Burrows (5046-5055).
In this paper, the NOx emission scaling factors applied over the 2001 National Emissions Inventory (NEI) are estimated through a four-dimensional variational (4D-Var) approach using SCIAMACHY (Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY) tropospheric NO2 columns measured during summer 2004. In the “top-down” approach, two-month average NO2 columns are assimilated into a regional chemical transport model (CTM), STEM, using different assimilation setups. In a basic setup, NOx emissions are adjusted by assimilating the NO2 columns. A more general setup of emission inversion allows the initial O3 concentrations be adjusted along with the NOx emissions. A final case is set up to assimilate both the NO2 columns and O3 measurement from various platforms while allowing adjustments of both the NOx emissions and the initial O3 concentrations. It is found that the addition of O3 measurements did not improve the NOx emission inversion. With the NOx emission at surface and upper levels being adjusted separately, results from four cases show that the elevated NOx emission reduction ranges from 8.9% to 11.4%, and the surface NOx emission reduction is up to 6.6%. All the cases show NOx emission reduction in Ohio valley and Washington, District of Columbia areas.
Keywords: NO2 column; NOx emission; Adjoint; Emission inversion; Assimilation;

Street canyon ventilation and atmospheric turbulence by P. Salizzoni; L. Soulhac; P. Mejean (5056-5067).
Operational models for pollutant dispersion in urban areas require an estimate of the turbulent transfer between the street canyons and the overlying atmospheric flow. To date, the mechanisms that govern this process remain poorly understood. We have studied the mass exchange between a street canyon and the atmospheric flow above it by means of wind tunnel experiments. Fluid velocities were measured with a Particle Image Velocimetry system and passive scalar concentrations were measured using a Flame Ionisation Detector. The mass-transfer velocity between the canyon and the external flow has been estimated by measuring the cavity wash-out time. A two-box model, used to estimate the transfer velocity for varying dynamical conditions of the external flow, has been used to interpret the experimental data. This study sheds new light on the mechanisms which drive the ventilation of a street canyon and illustrates the influence of the external turbulence on the transfer process.
Keywords: Street canyon; Turbulent mass transfer; Urban air pollution; Dispersion models;

PM composition and source reconciliation in Mexico City by V. Mugica; E. Ortiz; L. Molina; A. De Vizcaya-Ruiz; A. Nebot; R. Quintana; J. Aguilar; E. Alcántara (5068-5074).
PM2.5 and PM10 were collected during 24-h sampling intervals from March 1st to 31st, 2006 during the MILAGRO campaign carried out in Mexico City's northern region, in order to determine their chemical composition, oxidative activity and the estimation of the source contributions during the sampling period by means of the chemical mass balance (CMB) receptor model. PM2.5 concentrations ranged from 32 to 70 μg m−3 while that of PM10 did so from 51 to 132 μg m−3. The most abundant chemical species for both PM fractions were: OC, EC, SO4 2−, NO3 , NH4 +, Si, Fe and Ca. The majority of the PM mass was comprised of carbon, up to about 52% and 30% of the PM2.5 and PM10, respectively. PM2.5 constituted more than 50% of PM10. The redox activity, assessed by the dithiothreitol (DTT) assay, was greater for PM2.5 than for PM10, and did not display significant differences during the sampling period. The PM2.5 source reconciliation showed that in average, vehicle exhaust emissions were its most important source in an urban site with a 42% contribution, followed by re-suspended dust with 26%, secondary inorganic aerosols with 11%, and industrial emissions and food cooking with 10% each. These results had a good agreement with the Emission Inventory. In average, the greater mass concentration occurred during O3S that corresponds to a wind shift initially with transport to the South but moving back to the North. Taken together these results show that PM chemical composition, oxidative potential, and source contribution is influenced by the meteorological conditions.
Keywords: MILAGRO; Mexico City; PM; CMB; Receptor models; DTT;

Concentrations of traffic-related air pollution can be highly variable at the local scale and can have substantial seasonal variability. This study was designed to provide estimates of intra-urban concentrations of ambient nitrogen dioxide (NO2) in Montreal, Canada, that would be used subsequently in health studies of chronic diseases and long-term exposures to traffic-related air pollution. We measured concentrations of NO2 at 133 locations in Montreal with passive diffusion samplers in three seasons during 2005 and 2006. We then used land use regression, a proven statistical prediction method for describing spatial patterns of air pollution, to develop separate estimates of spatial variability across the city by regressing NO2 against available land-use variables in each of these three periods. We also developed a “pooled” model across these sampling periods to provide an estimate of an annual average. Our modelling strategy was to develop a predictive model that maximized the model R 2. This strategy is different from other strategies whose goal is to identify causal relationships between predictors and concentrations of NO2.Observed concentrations of NO2 ranged from 2.6 ppb to 31.5 ppb, with mean values of 12.6 ppb in December 2005, 14.0 ppb in May 2006, and 8.9 ppb in August 2006. The greatest variability was observed during May. Concentrations of NO2 were highest downtown and near major highways, and they were lowest in the western part of the city. Our pooled model explained approximately 80% of the variability in concentrations of NO2. Although there were differences in concentrations of NO2 between the three sampling periods, we found that the spatial variability did not vary significantly across the three sampling periods and that the pooled model was representative of mean annual spatial patterns.
Keywords: Nitrogen dioxide; Land use regression; Geographic information systems;

An evaluation of measurement methods for organic, elemental and black carbon in ambient air monitoring sites by Paul Quincey; David Butterfield; David Green; Mhairi Coyle; J. Neil Cape (5085-5091).
The carbonaceous components of Particulate Matter samples form a substantial fraction of their total mass, but their quantification depends strongly on the instruments and methods used. United Kingdom monitoring networks have provided many relevant data sets that are already in the public domain. Specifically, hourly organic carbon (OC) and elemental carbon (EC) were determined at four sites between 2003 and 2007 using Rupprecht and Pattashnik (R & P) 5400 automatic instruments. Since 2007, daily OC/EC measurements have been made by manual thermo-optical analysis of filter samples using a Sunset Laboratory Carbon Aerosol Analysis instrument. In parallel, long term daily measurements of Black Smoke, a quantity directly linked to black carbon (measured by aethalometers) and indirectly related to elemental carbon, have been made at many sites. The measurement issues associated with these techniques are evaluated in the context of UK measurements, making use of several sets of parallel data, with the aim of aiding the interpretation of network results. From the results available, the main conclusions are that the R & P 5400 instruments greatly under-read EC and total carbon (TC = OC + EC) at kerbside sites, probably due to the fact that the smaller particles are not sampled by the instrument; the R & P 5400 instrument is inherently difficult to characterise, so that all quantitative results need to be treated with caution; both aethalometer and Black Smoke (converted to black carbon) measurements can show reasonable agreement with elemental carbon results; and manual thermo-optical OC/EC results may under-read EC (and hence over-read OC), whether either transmittance or reflectance is used for the pyrolysis correction, and this effect is significant at rural sites.
Keywords: Black Smoke; Black carbon; Organic carbon; Elemental carbon; Air quality; UK;

Estimating Taiwan biogenic VOC emission: Leaf energy balance consideration by Ken-Hui Chang; Jhih-Yuan Yu; Tu-Fu Chen; Yi-Pin Lin (5092-5100).
The goal of the present study is to provide a comprehensive model to estimate biogenic volatile organic compounds (BVOCs) in Taiwan. In addition to metrological data, the model consists of (1) 83 land-use patterns, (2) emission factors for various vegetations, (3) energy balance equation to account for leaf temperature, and (4) correction terms for photosynthetically active radiation. The model output includes 4 categories of 33 BVOCs [isoprene, methylbutenol (MBO), 14 species of monoterpenes and 17 other BVOCs]. The results of model verification based on several approaches include: (1) predicted isoprene emission flux correlates relatively good with the observed isoprene concentration (R 2  = 0.66); (2) correlation between leaf temperature and observed isoprene levels is better than that between ambient temperature and isoprene concentrations (R 2  = 0.63 vs. 0.58); (3) model-predicted isoprene fluxes match well with observed 3-day diurnal isoprene concentration variations; and (4) subsequent model-predicted O3 concentrations with the BVOC input obtained in the present study match well than that with previous estimated BVOC data with the observed 6-day diurnal O3 levels in 8 air quality monitoring stations.Based on the meteorological data in 2000, the total emission of BVOCs in Taiwan was simulated to be about 433,000 ton (33% of total VOCs) of which both isoprene and 14 species of monoterpenes account for about 34%, with 17 species of other BVOCs being 31% and <2% contribution from MBO. Total emissions of BVOCs are higher in lower and medium altitude (300–1000 m) mountain areas with an average of around 15–30 ton km−2  y−1. The implication of the other results is also discussed.
Keywords: BVOCs; Isoprene; Leaf temperature; Land use; O3;

In this paper we examine the effect of different roadway configurations, including noise barriers and roadway elevation or depression relative to the surrounding terrain, on the dispersion of traffic-related pollutants for winds perpendicular to the roadway. A wind tunnel experiment modeling 12 different configurations was performed to study the flow fields and the concentration distributions resulting from emissions from a simulated six-lane highway. All of the configurations examined here reduced the downwind ground-level concentrations relative to that for a flat, unobstructed roadway; however, the degree to which the concentrations were reduced varied widely depending on the particular situation.Ground-level concentration data from the cases considered in this research indicate that a constant entrainment velocity can be used over the region beginning downwind of any initial disturbance to the flow resulting from the roadway configuration (e.g., a recirculation region behind a noise barrier) and extending at least to the end of our measurements. For example, for the case of a single noise barrier on the downwind side of the road, this region extends from approximately four barrier heights downwind of the roadway to 40 barrier heights. It was also found that the virtual origin concept is useful in describing the initial mixing created by the particular roadway configuration. To effectively model the influence of the roadway configuration on the dispersion, a combination of a virtual origin and an entrainment velocity may be effective. The magnitude of the virtual origin shift appears to depend on the particular roadway configuration, while the entrainment velocity appears to be a function of the friction velocity and the roadway geometry. These results suggest that road configuration must be taken into account in modeling near-road air quality.
Keywords: Air quality; Line source; Dispersion modeling; Wind tunnel; Roadway configurations;

A highly resolved temporal and spatial Pearl River Delta (PRD) regional emission inventory for the year 2006 was developed with the use of best available domestic emission factors and activity data. The inventory covers major emission sources in the region and a bottom–up approach was adopted to compile the inventory for those sources where possible. The results show that the estimates for SO2, NOx, CO, PM10, PM2.5 and VOC emissions in the PRD region for the year 2006 are 711.4 kt, 891.9 kt, 3840.6 kt, 418.4 kt, 204.6 kt, and 1180.1 kt, respectively. About 91.4% of SO2 emissions were from power plant and industrial sources, and 87.2% of NOx emissions were from power plant and mobile sources. The industrial, mobile and power plant sources are major contributors to PM10 and PM2.5 emissions, accounting for 97.7% of the total PM10 and 97.2% of PM2.5 emissions, respectively. Mobile, biogenic and VOC product-related sources are responsible for 90.5% of the total VOC emissions. The emissions are spatially allocated onto grid cells with a resolution of 3 km × 3 km, showing that anthropogenic air pollutant emissions are mainly distributed over PRD central-southern city cluster areas. The preliminary temporal profiles were established for the power plant, industrial and on-road mobile sources. There is relatively low uncertainty in SO2 emission estimates with a range of −16% to +21% from power plant sources, medium to high uncertainty for the NOx emissions, and high uncertainties in the VOC, PM2.5, PM10 and CO emissions.
Keywords: Emission inventory; Temporal; Spatial; Uncertainty; PRD region;

Real-time wet scavenging of major chemical constituents of aerosols and role of rain intensity in Indian region by U.C. Kulshrestha; L.A.K. Reddy; J. Satyanarayana; Monika J. Kulshrestha (5123-5127).
Real-time simultaneous studies on chemical characteristics of rainwater and PM10 aerosols were carried out to understand the scavenging of major chemical components in Indian region. The concentrations of Ca2+, NH4 +, SO4 2− and NO3 were observed to be lower in the aerosol samples collected during rain as compared to before and after rain events. The most significant reduction was noticed for Ca2+ (74%) during rain which showed highest scavenging ratio (SR) and indicated that below-cloud scavenging is an effective removal process for Ca2+ in Indian region. Among non-sea salt components, Ca2+ had highest SR at Hyderabad indicating typical characteristics of crustal influence as abundance of calcium carbonate in soil dust has been reported in India. However, the levels of these major chemical components gradually got build-up in due course of time. After rain events, the levels of SO4 2− aerosols were noticed to be substantially higher (more than double) within 24 h. In general, scavenging ratios for all components (except Ca2+, NH4 + and K+) were higher over BOB as compared to Hyderabad. The maximum fall in aerosol levels (BR minus AR) was observed during continuous and low intensity rain events that did not allow building up of aerosol concentrations.
Keywords: Wet scavenging of aerosols; Crustal components; Scavenging ratios; Anthropogenic aerosols; Rain intensity; PM10 aerosols;

Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas? by Justin M. Langridge; R. Joel Gustafsson; Paul T. Griffiths; R. Anthony Cox; Richard M. Lambert; Roderic L. Jones (5128-5131).
The photoenhanced uptake of nitrogen dioxide (NO2) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO2) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO2 and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO2 materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO2 to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NOx as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.
Keywords: Nitrous acid; NOx; Titanium dioxide; Self-cleaning window glass; Air quality;