Atmospheric Environment (v.43, #25)

High bromine oxide concentrations in the semi-polluted boundary layer by Anoop S. Mahajan; Hilke Oetjen; James D. Lee; Alfonso Saiz-Lopez; Gordon B. McFiggans; John M.C. Plane (3811-3818).
Bromine chemistry in the marine boundary layer is recognized to play an important role through catalytic ozone destruction, changes to the atmospheric oxidising capacity (by changing the OH/HO2 and NO/NO2 ratio) and oxidation of compounds such as dimethyl sulphide (DMS). However, the chemistry of bromine in polluted environments is not well understood and its effects are thought to be inhibited by reactions involving NO x (NO2 & NO). This paper describes long-path Differential Optical Absorption Spectroscopy (DOAS) observations of bromine oxide (BrO) at a semi-polluted coastal site in Roscoff, France. Significant concentrations of BrO (up to 7.5 ± 1.0 pptv) were measured during daytime, indicating the presence of unknown sources or efficient recycling of reactive bromine from bromine nitrate (BrONO2), which should be the major reservoir for bromine in a high NO x environment. These measurements indicate that bromine chemistry can play an important role in polluted environments.
Keywords: Differential optical absorption; Bromine oxide; Ozone depletion; Marine boundary layer;

Quality considerations of European PM emission inventories by Wilfried Winiwarter; Thomas A.J. Kuhlbusch; Mar Viana; Regina Hitzenberger (3819-3828).
This paper reviews information on emission inventories of particulate matter (PM) in Europe. A large body of scientific literature is available to cover many different aspects. Studies focus on specific sources or source sectors (road transport as well as off-road machinery, domestic heating, industry, agriculture, and natural sources), among which especially road transport emissions are clearly best established. Emission inventories comprising all sources are available for specific European regions, often pointing out regional differences, but also for the entire continent. Still these inventories often are not able to satisfy the needs. Due to PM specific circumstances such as the large number of sources, very different release pathways and differences of the individual particles in terms of chemical composition or size, it is very difficult to appropriately handle measurement conditions to arrive at adequate emission factors, especially when emission points cannot be defined clearly. Information on fugitive emissions (caused by wind shear, material transfer processes or other mechanical forces from non-point sources) is sparse, except for road traffic emissions where recent data seems to converge. The problem of data gaps concerns activities in industry (quarries), agriculture, but also natural particles like sea salt and wind-blown dust. Comparing complete inventories to independent efforts in assessing emissions, e.g. atmospheric measurements combined with source apportionment, allows to better understand and quantify the reliability of inventory data. Methodological improvements and harmonization currently under way in Europe will focus efforts and allow for more reliable PM inventories in the near future.
Keywords: Particulate matter; Fugitive sources; Outlook; Review; Europe;

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps, cluster, and Principal Component Analysis by Gabriel Ibarra-Berastegi; Jon Sáenz; Agustín Ezcurra; Unai Ganzedo; Javier Díaz de Argandoña; Iñigo Errasti; Alejandro Fernandez-Ferrero; Josué Polanco-Martínez (3829-3836).
In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO2 fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO2 measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.
Keywords: Sulphur dioxide; Air quality network; Fluid mechanics; Applied physics; R;

Identification of redundant air quality measurements through the use of principal component analysis by J.C.M. Pires; M.C. Pereira; M.C.M. Alvim-Ferraz; F.G. Martins (3837-3842).
This study aims to show how principal component analysis (PCA) can be used to identify redundant measurements in air quality monitoring networks. The minimum number of air quality monitoring sites in Oporto Metropolitan Area (Oporto-MA) was evaluated using PCA and then compared to the one settled by the legislation. Nine sites, monitoring NO2, O3 and PM10, were selected and the air pollutant concentrations were analysed from January 2003 to December 2005. PCA was applied to the data corresponding to the first two years that were divided into annual quarters to verify the persistence of the PCA results. The number of principal components (PCs) was selected by applying two criteria: Kaiser (PCs with eigenvalues greater than 1) and ODV90 (PCs representing at least 90% of the original data variance). Each pollutant was analysed separately. The two criteria led to different results. Using Kaiser criterion for the eight analysed periods, two PCs were selected in: (i) five periods for O3 and PM10; and (ii) six periods for NO2. These PCs had important contributions of the same groups of monitoring sites. The percentage of the original data variance contained in the selected PCs using this criterion was always below 90%. Thus, the results obtained using ODV90 were considered with more confidence. Using this criterion, only five monitoring sites for NO2, three for O3 and seven for PM10 were needed to characterize the region. The number of monitoring sites for NO2 and O3 was in agreement with what was established by the legislation. However, for PM10, Oporto-MA needed two more monitoring sites. To validate PCA results, statistical models were determined to estimate air pollutant concentrations at removed monitoring sites using the concentrations measured at the remaining monitoring sites. These models were applied to a year's data. The good performance obtained by the models showed that the monitoring sites selected by the procedure presented in this study were enough to infer the air pollutant concentrations in the region defined by the initial monitoring sites. Additionally, the air pollutant analysers corresponding to the redundant measurements can be installed in non-monitored regions, allowing the enlargement of the air quality monitoring network.
Keywords: Principal component analysis; Air quality monitoring network management; Redundant measurements;

Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers by Chakra Chaemfa; Jonathan L. Barber; Kyoung-Sim Kim; Tom Harner; Kevin C. Jones (3843-3849).
Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm−3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ∼6.5 m3 day−1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ∼8 m3 day−1 for PCB-52; ∼9.5 m3 day−1 for PCB-95; ∼11 m3 day−1 for BDE-28 and ∼2 m3 day−1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.
Keywords: Passive sampler; Polyurethane foam; Uptake rates; Persistent organic pollutants;

The present study examines the behaviour of the ADMS-Urban air quality forecasting model in predicting dispersion of traffic-related pollutants in urban areas. The study has been carried out in Ravenna (NE Italy), a medium-sized town where pollution produced by vehicle traffic accounts for most of the emissions. ADMS-Urban performances have been assessed through statistical analysis, by comparing carbon monoxide concentrations (vehicle traffic tracing pollutant) estimated by the model with concentrations measured by stations of the air quality monitoring network. Although the correspondence of values estimated by ADMS-Urban with measured values turns out to be satisfactory, the study shows that the model tends to produce an underestimated value compared with the actual situation, and identifies a corrective method that makes it possible to improve the relevant performances. Furthermore, the diagnostic analysis highlights that the model performances depend upon some meteorological parameters.
Keywords: ADMS-Urban; Carbon monoxide; Statistical analysis; Diagnostic analysis; Traffic pollution;

The extent of the exceedance of the EU limit values for nitrogen dioxide (NO2) and particulate matter (PM10) concentrations within the Netherlands is expected to decrease significantly, in the coming years. Whether limit values will actually be exceeded, in the next decade, depends not only on European, national and local policies, but also on the effects of inevitable interannual meteorological fluctuations. An analysis of model calculations and measurements yields variations (1 sigma) in the annual average concentration of about 5% for NO2 and 9% for PM10, due to meteorological fluctuations. These deviations from long-term average concentrations affect assessments of future levels, set against limit values. For instance, an NO2 concentration of 39 μg m−3, estimated for a given year with long-term average meteorology, indicates that it is likely (chance >66%) that the limit value of 40 μg m−3 will not be exceeded in that particular year. At the same time, the estimation also indicates, for example, that this situation is unlikely (change <33%) to continue for three years in a row. However, with an estimated concentration of 38 μg m−3, it is likely that the limit value will not be exceeded for three years in a row. The limit value for the daily average PM10 concentration is equivalent to an annual average of about 32 μg m−3. This threshold is unlikely to be exceeded for three years in a row, when an annual average concentration of 29 μg m−3 is estimated. Interannual variations in concentrations of NO2 and PM10 are linked to large-scale meteorological fluctuations. Therefore, similar results can be expected for other European countries.
Keywords: Air quality; Nitrogen dioxide; Particulate matter; Interannual; Measurements;

In this study, we measured the wet deposition fluxes of ten trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb, Sb, V and Zn) from December 2002 to March 2006 at three sites along the Japan Sea coast, which have been strongly affected by the long-range transport of air pollutants from the Asian continent. Also, factors, contributing to their seasonal variations were investigated. At the northern and central sites, the monthly wet deposition fluxes of all or most trace elements greatly increased during the cold season (typically, November–April), along with their monthly average (volume-weighted) concentrations in the precipitation. The cold/warm season ratios for the average concentrations of trace elements in precipitation were within the range of 2.7–5.1 at the northern site and 1.8–5.9 at the central site, which were similar to the average scavenging ratios (= concentration in precipitation/concentration in air) at each site. However, there were small differences (0.47–1.2 at the northern site and 0.73–1.7 at the central site) in the ratios of average concentrations in air between the two seasons. These suggest that the increase in the wet deposition fluxes of trace elements during the cold season is due to increases in their scavenging ratios. On the other hand, the result for the southern site was different from those at the other sites. The number of days when the daily maximum wind speed exceeded 10 m s−1 at the meteorological observatories near the study sites increased markedly during the cold season at the northern and central sites, showing that strong winds usually blow during the cold season at those sites, but not at the southern site. Higher wind speed transports larger amounts of constituents into the cloud system, which can result in their increased concentrations in precipitation. Thus, high scavenging ratios of trace elements during the cold season may be caused by the increase in their amounts of discharge into the cloud system owing to high wind speed, suggesting that wind speed is an important factor in the seasonal variations in the wet deposition fluxes.
Keywords: Precipitation; Scavenging ratio; Asian continent; Long-range transport of air pollutants; Wind speed;

Single particle mass spectrometry of oxalic acid in ambient aerosols in Shanghai: Mixing state and formation mechanism by Fan Yang; Hong Chen; Xinning Wang; Xin Yang; Jianfei Du; Jianmin Chen (3876-3882).
Oxalic acid in individual aerosol particles was measured using single particle aerosol time-of-flight mass spectrometry (ATOFMS) in the summer of 2007 in Shanghai, China. Oxalate was found in 3.4% of total particles with diameters in the range of 0.2 – 2.0 μm. Size, chemical composition and hourly temporal counts of single particles that contained oxalic acid were measured. The predominant types of oxalate-containing particles were characterized to distinguish the primary and secondary sources of oxalic acid. Biomass burning was revealed as a major primary source of oxalic acid which contributed more than 20% of the oxalate-containing particles. Evidences for two different formation pathways of oxalic acid were observed in our experiment. The number fraction of oxalate-containing particles correlated with that of sulfate particles and the changes of air parcel backward trajectories, suggesting that in-cloud processing played important roles in oxalic acid formation. The diurnal patterns of dust and sea salt particle counts fitted well with the ambient relative humidity variation, suggesting that heterogeneous reactions occurring in hydrated/deliquesced aerosols also contributed to the production of oxalic acid.
Keywords: Oxalic acid; ATOFMS; Mixing state; Formation mechanism;

Emission factors of particulate-bound Polycyclic Aromatic Hydrocarbons (PAHs) including benzo(a)pyrene and, for the first time, the highly carcinogenic dibenzo(a,l)pyrene, dibenzo(a,e)pyrene, dibenzo(a,i)pyrene and dibenzo(a,h)pyrene have been determined in exhausts from two diesel- (DFVs) and two gasoline-fuelled light-duty vehicles (GFVs) operated in the Urban (AU), Rural Road (AR) and Motorway (AM) transient ARTEMIS driving cycles. The obtained results showed the DFVs to emit higher amounts of PAHs than the GFVs per km driving distance at low average speed in the AU driving cycle, while the GFVs emitted higher amounts of PAHs than the DFVs per km driving distance at higher average speeds in the AR and AM driving cycles. Furthermore, the study showed an increase in PAH emissions per km driving distance with increasing average speed for the GFVs with the opposite trend found for the DFVs. The GFVs generated particulate matter with higher PAH content than the DFVs in all three driving cycles tested with the highest concentrations obtained in the AR driving cycle. Dibenzo(a,l)pyrene was found to be a major contributor to the potential carcinogenicity accounting for 58–67% and 25–31% of the sum added potential carcinogenicity of the measured PAHs in the emitted particulate matter from the DFVs and GFVs, respectively. Corresponding values for benzo(a)pyrene were 16–25% and 11–40% for the DFVs and GFVs, respectively. The DFVs displayed higher sum added potential carcinogenicity of the measured PAHs than the GFVs in the AU driving cycle with the opposite trend found in the AR and AM driving cycles. The findings of this study show the importance of including the dibenzopyrenes in vehicle exhaust chemical characterizations to avoid potential underestimation of the carcinogenic activity of the emissions. The lower emissions and the lower sum added potential carcinogenicity of the measured PAHs found in this study for the GFVs compared to the DFVs in the AU driving cycle indicate the GFVs to be preferred in dense urban areas with traffic moving at low average speeds with multiple start and stops. However, the obtained results suggest the opposite to be true at higher average speeds with driving at rural roads and motorways. Further studies are, however, needed to establish if the observed differences between GFVs and DFVs are generally valid as well as to study the effects on variations in vehicle/engine type, ambient temperature, fuel and driving conditions on the emission factors.
Keywords: Regulated emissions; Particle emissions; Unregulated emissions; Gasoline; Diesel; Light-duty vehicles; PAH; Benzo(a)pyrene; Dibenzopyrenes; Dibenzo(a,l)pyrene; Toxic Equivalency Factor; TEF;

A modeling assessment of association between East Asian summer monsoon and fate/outflow of α-HCH in Northeast Asia by Chongguo Tian; Jianmin Ma; Liyan Liu; Hongliang Jia; Diandou Xu; Yi-Fan Li (3891-3901).
Using a dynamic numerical atmospheric transport model for organochlorine pesticides (OCPs), the relationship between the East Asian summer monsoon and the fate of α-hexachlorocyclohexane (α-HCH), a banned OCP, in the atmosphere over Northeast Asia was investigated and assessed. The modeled temporal and spatial patterns and variability of α-HCH air concentrations during the summer months of 2005 revealed a strong link between this chemical in the atmosphere over Northeast Asia and the East Asian summer monsoon. At lower atmospheric levels, easterly and southeasterly winds blowing from relatively cold ocean surface convey α-HCH air concentration from southeast China to northeast China. A monsoon front extending from southeast China to Japan, characterized by a strong wind convergence, carried the air concentration to a high elevation of the atmosphere where it was delivered by southerly monsoon flow to northern China and North Pacific Ocean. This summer monsoon associated northward atmospheric transport caused a reversal of the soil/air exchange from outgassing to net deposition during spring–summer period. The modeled wet deposition fluxes of α-HCH agreed well with the changes in the typical summer monsoon rain bands, designated as Meiyu in China, Changma in Korea, and Baiu in Japan. The major wet deposition flux paralleled with the monsoon front as well as the monsoon rain bands. The temporal change in the fluxes exhibits abrupt northward advances, which is associated with a stepwise northward and northeastward advance of the East Asian summer monsoon. The modeled α-HCH outflow in the atmosphere from China occurs mostly in the summer months and through northeast China, featured strongly by the evolution of the summer month. This study suggests that the East Asian summer monsoon provides a major atmospheric pathway and summer outflows to α-HCH over East Asia.
Keywords: Organochlorine pesticide; α-HCH; Summer monsoon; Northeast Asia;

The purpose of this paper is to identify the atmospheric conditions associated with elevated ground-level ozone concentrations during June–August of 2000–2007 at 11 ozone-monitoring stations in the Atlanta, GA, USA metropolitan statistical area (MSA). Analyses were confined to high-ozone days (HODs), which had a daily maximum 8-h average ozone concentration in the 95th percentile of all June–August values. Therefore, each station had 36 HODs. The southeastern and far northern portions of the MSA had HODs with the highest and lowest ozone concentrations, respectively. HODs at nearly all Atlanta MSA ozone-monitoring stations were enabled by migratory anticyclones. HODs for most stations were hot, dry, and calm with low morning mixing heights and high afternoon mixing heights. All sets of HODs had daily mean relative humidities and afternoon mixing heights that, respectively, were significantly less than and significantly greater than mean values for the remaining days. Urbanized Atlanta typically was upwind of an ozone-monitoring station on its HODs; therefore, wind direction on HODs varied considerably among the stations. HODs may have been caused partially by NO x emissions from electric-utility power plants: HODs in the southern portion of the MSA were linked to air-parcel trajectories intersecting a power plant slightly northwest of Atlanta and plants in the Ohio River Valley, while HODs in the northern portion of the MSA were linked to air-parcel trajectories intersecting two large power plants slightly southeast of the Atlanta MSA. Results from this study suggest that future research in the Atlanta MSA should focus on power-plant contributions to ground-level ozone concentrations as well as the identification of non-monitored locations with potentially high ozone concentrations.
Keywords: Ozone; Atlanta; Southeastern United States; Trajectory; NAAQS;

Microenvironmental characteristics important for personal exposures to aldehydes in Sacramento, CA, and Milwaukee, WI by J.H. Raymer; G. Akland; T.R. Johnson; T. Long; L. Michael; L. Cauble; M. McCombs (3910-3917).
Oxygenated additives in gasoline are designed to decrease the ozone-forming hydrocarbons and total air toxics, yet they can increase the emissions of aldehydes and thus increase human exposure to these toxic compounds. This paper describes a study conducted to characterize targeted aldehydes in microenvironments in Sacramento, CA, and Milwaukee, WI, and to improve our understanding of the impact of the urban environment on human exposure to air toxics. Data were obtained from microenvironmental concentration measurements, integrated, 24-h personal measurements, indoor and outdoor pollutant monitors at the participants' residences, from ambient pollutant monitors at fixed-site locations in each city, and from real-time diaries and questionnaires completed by the technicians and participants. As part of this study, a model to predict personal exposures based on individual time/activity data was developed for comparison to measured concentrations. Predicted concentrations were generally within 25% of the measured concentrations. The microenvironments that people encounter daily provide for widely varying exposures to aldehydes. The activities that occur in those microenvironments can modulate the aldehyde concentrations dramatically, especially for environments such as “indoor at home.” By considering personal activity, location (microenvironment), duration in the microenvironment, and a knowledge of the general concentrations of aldehydes in the various microenvironments, a simple model can do a reasonably good job of predicting the time-averaged personal exposures to aldehydes, even in the absence of monitoring data. Although concentrations of aldehydes measured indoors at the participants' homes tracked well with personal exposure, there were instances where personal exposures and indoor concentrations differed significantly. Key to the ability to predict exposure based on time/activity data is the quality and completeness of the microenvironmental characterizations for the chemicals of interest. Consistent with many earlier studies, personal exposures are difficult to predict using data from regional outdoor monitors.
Keywords: Urban air toxics; Aldehydes; Personal exposure; Time/activity modeling; Microenvironmental exposure;

Knowledge of the distribution and sources of black carbon (BC) is essential to understanding its impact on radiative forcing and the establishment of a control strategy. In this study, we analyze atmospheric BC and its relationships with fine particles (PM2.5) and trace gases (CO, NO y and SO2) measured in the summer of 2005 in two areas frequently influenced by plumes from Beijing and Shanghai, the two largest cities in China. The results revealed different BC source characteristics for the two megacities. The average concentration of BC was 2.37 (±1.79) and 5.47 (±4.00) μg m−3, accounting for 3.1% and 7.8% of the PM2.5 mass, in Beijing and Shanghai, respectively. The good correlation between BC, CO and NO y (R 2 = 0.54–0.77) and the poor correlation between BC and SO2 suggest that diesel vehicles and marine vessels are the dominant sources of BC in the two urban areas during summer. The BC/CO mass ratio in the air mass from Shanghai was found to be much higher than that in the air mass from Beijing (0.0101 versus 0.0037 ΔgBC/ΔgCO), which is attributable to a larger contribution from diesel burning (diesel-powered vehicles and marine vessels) in Shanghai. Based on the measured ratios of BC/CO and annual emissions of CO, we estimate that the annual emissions of BC in Beijing and Shanghai are 9.51 Gg and 18.72 Gg, respectively. The improved emission rates of BC will help reduce the uncertainty in the assessment of the impact of megacities on regional climate.
Keywords: PM2.5; Black carbon; Trace gases; Emission; Beijing; Shanghai;

Retrospective assessment of air quality management practices in Taiwan by Pei-Hsuan Kuo; Pei-Chen Ni; Andrew Keats; Ben-Jei Tsuang; Yung-Yao Lan; Min-Der Lin; Chien-Lung Chen; Yueh-Yuan Tu; Len-Fu Chang; Ken-Hui Chang (3925-3934).
In 1995, Taiwan's Environmental Protection Administration (EPA/TW) instituted a policy of levying emission taxes on polluters in order to combat the rampant national issue of pollution. Since that time, pollution control strategies, tightening exhaust emission standards for industry, improvements in fuel quality, and new stricter vehicle emission standards, etc., have been implemented. This study evaluates the effectiveness of these measures and examines the improvement of Taiwan's air quality. In this paper, we conduct a detailed analysis of change in the concentrations of pollutants (SO2, NO x and particulate matter [PM]) between two three-year periods (from 1996 to1998 and from 2000 to 2002). The pollution levels were generally lower in the latter period. Concentrations at 14 EPA/TW stations in central Taiwan were simulated and source apportionment analyses in three of Central Taiwan's largest cities were conducted using a trajectory transfer-coefficient air quality model. Correlation coefficients (r) between simulations and observations for the monthly means of the concentrations of SO2, NO x , PM2.5 and PM10 during the study periods at the 14 stations are 0.56, 0.63, 0.70 and 0.31, respectively. The sulfur control policy greatly reduced SO2 concentration island-wide, a stringent emission standard put into place for gasoline vehicles reduced NO x concentration along highways, and an emissions tax placed on construction sites, as well as a regular program for road-dust sweeping, reduced primary particulate matter. Among all of the pollution abatement policies implemented, the most effective method for reducing PM2.5 concentrations in the three largest cities involved the reduction of fine ammonium sulfate aerosols from point sources (56–63% of net PM2.5 reduction). The next largest reduction was attributed to a diminishment in primary PM2.5 emanating from point sources (27–56% of net PM2.5 reduction). Secondary particulate matter, especially sulfate, was reduced from distances up to 150 km leeward of major pollution point sources such as Taichung Power Plant.
Keywords: Air quality model; Source apportionment; Gaussian plume model; Emission controls;

The formation of secondary organic aerosol (SOA) produced from linalool ozonolysis was examined using a dynamic chamber system that allowed the simulation of ventilated indoor environments. Experiments were conducted under room temperature (22–23 °C) and air exchange rate of 0.67 h−1. An effort was made to maintain the product of the concentrations of the two reagents constant. The results suggest that under the conditions when the product of the two reagent concentrations was constant, the relative concentrations play an important role in determining the total SOA formed. A combination of concentrations somewhere in ozone limiting region will produce the maximum SOA concentration. The measured reactive oxygen species (ROS) concentrations at linalool and ozone concentrations relevant to prevailing indoor concentrations ranged from 0.71 to 2.53 nmol m−3 equivalents of H2O2. It was found that particle samples aged for 24 h lost a significant fraction of the ROS compared to fresh samples. The residual ROS concentrations were around 15–69%. Compared with other terpene species like α-pinene that has one endocyclic unsaturated carbon bond, linalool was less efficient in potential SOA formation yields.
Keywords: Linalool; SOA; ROS; Indoor aerosol; Yield;

Apportioning black carbon to sources using highly time-resolved ambient measurements of organic molecular markers in Pittsburgh by Andrew T. Lambe; Jennifer M. Logue; Nathan M. Kreisberg; Susanne V. Hering; David R. Worton; Allen H. Goldstein; Neil M. Donahue; Allen L. Robinson (3941-3950).
We present highly time-resolved measurements of organic molecular markers in downtown Pittsburgh, which are used to investigate sources contributing to atmospheric aerosols in the area. Two-hour average concentrations of condensed-phase and semivolatile organic species were measured using a Thermal Desorption Aerosol GC/MS (TAG). Concentrations for mobile source markers like hopanes had regular diurnal and day-of-week patterns. Pairing high time-resolved measurements with meteorological data helped identify contributions from known point sources for markers correlated with wind direction. Black carbon (BC), volatile organic compounds (VOCs) and organic molecular markers were apportioned to sources using the Chemical Mass Balance (CMB) and Positive Matrix Factorization (PMF) receptor models. Diesel and gasoline mobile source factors were identified as the main sources of BC in the downtown Pittsburgh area, contributing 67% and 20% of the study-average BC. 13% of the BC was associated with a source factor tentatively identified as an industrial or regional source. The high time resolution of the TAG has the potential to provide important new insight into source apportionment efforts using organic molecular marker measurements.
Keywords: Organic aerosols; Black carbon; Molecular markers; Thermal desorption aerosol GC/MS (TAG); Source apportionment; PMF; CMB;

Probing the sensitivity of gaseous Br2 production from the oxidation of aqueous bromide-containing aerosols and atmospheric implications by Paul Nissenson; Daniel M. Packwood; Sherri W. Hunt; Barbara J. Finlayson-Pitts; Donald Dabdub (3951-3962).
This paper presents a global sensitivity and uncertainty analysis of the bromine chemistry included in the Model of Aqueous, Gaseous and Interfacial Chemistry (MAGIC) in dark and photolytic conditions. Uncertainty ranges are established for input parameters (e.g. chemical rate constants, Henry's law constants, etc.) and are used in conjunction with Latin hypercube sampling and multiple linear regression to conduct a sensitivity analysis that determines the correlation between each input parameter and model output. The contribution of each input parameter to the uncertainty in the model output is calculated by combining results of the sensitivity analysis with input parameters' uncertainty ranges. Model runs are compared using the predicted concentrations of molecular bromine since Br2(g) has been shown in previous studies to be generated via an interface reaction between O3(g) and Br(surface) during dark conditions [Hunt et al., 2004]. Formation of molecular bromine from the reaction of ozone with deliquesced NaBr aerosol: evidence for interface chemistry. Journal of Physical Chemistry A 108, 11559–11572]. This study also examines the influence of an interface reaction between OH(g) and Br(surface) in the production of Br2(g) under photolytic conditions where OH(g) is present in significant concentrations. Results indicate that the interface reaction between O3(g) and Br(surface) is significant and is most responsible for the uncertainty in MAGICs ability to calculate precisely Br2(g) under dark conditions. However, under photolytic conditions the majority of Br2(g) is produced from a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transport.
Keywords: Interface chemistry; Bromide oxidation; Sensitivity analysis; Aerosol modeling;

Suspended atmospheric particles were collected in Israel in order to identify their nature and relationships with the major synoptic-scale circulation patterns. The particles were analyzed for their major and trace element concentrations and mineralogical composition. Samples were collected during three synoptic systems associated with desert dust storms: Red Sea trough, Sharav cyclone and cold depression, and during deep and shallow modes of Persian Gulf trough, which prevails in the summer months and is not associated with dust storms.All samples mostly contain particles smaller than 2 μm. The suspended desert dust is composed primarily of illite–smectite and calcite. Some indicative secondary minerals were found for each of the dust transporting synoptic systems (e.g., palygorskite for Red Sea trough). The bulk chemistry data support the mineralogical observations and reveal additional chemical signatures of each dust transporting system. For instance, Red Sea trough samples have significantly higher Ca/Al and Ca/Mg in the carbonate and Mg/Al in Al-silicate fraction than cold depression samples. Nevertheless, Sharav cyclone samples have intermediate values in spite of the fact that the source of the dust during these conditions is similar to cold depression (i.e., North Africa). Even though differences in the chemical and the mineralogical composition of desert dust do exist, this study reveals their overall chemical and mineralogical similarities.In contrast to the synoptic systems that carry desert dust, the inorganic fraction of the Persian Gulf trough samples contains significant amount (up to 50%) of non-mineral material that has a pronounced chemical signature in terms of major element concentrations (e.g., Al, Ca, Mg, Na, S) implying their anthropogenic nature, probably from countries around the Black Sea. This striking finding is indicative for atmospheric pollution in the Eastern Mediterranean region during the summer.
Keywords: Suspended desert dust; Pollution; Mineralogy;