Atmospheric Environment (v.39, #40)

Copper complexation in marine and terrestrial rain water by Melanie Witt; Tim Jickells (7657-7666).
The complexation of copper was studied in rainwater collected in Norwich, UK, and during Atlantic and Indian Ocean cruises. The complexation was measured with Chelex resin, Sep-Pak columns and adsorptive cathodic stripping voltammetry with tropolone as a competing ligand. Strong organic complexation was observed in semi-urban and marine rain samples with conditional stability constants between 1011 and 1014. Model solutions of copper and humic matter found organic complexes of a similar strength to those observed in the rain samples suggesting humic material as a potential ligand. A large proportion of the copper in the rains was associated with strong organic complexes over the pH range 4–8 in both filtered and unfiltered rain samples suggesting organic complexation is an important process both in the atmosphere and on arrival to oceans.
Keywords: Speciation; Humic; Tropolone; Chelex; PH;

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether ( k 297 K = 1.5 ( ± 1.7 ) × 1 0 9 M - 1 s - 1 , E a / R = 580 (±560) K), n-butyl acetate ( k 297 K = 1.8 (±0.4)×109  M−1  s−1, E a / R = 1000 (±200) K), acetone ( k 298 K = 0.11 (±0.05)×109  M−1  s−1, E a / R = 1400 (±500) K), methyl ethyl ketone ( k 298 K = 0.81 ( ± 0.18 ) × 1 0 9 M - 1 s - 1 , E a / R = 1200 (±200) K), methyl iso-butyl ketone ( k 298 K = 2.1 ( ± 0.5 ) × 1 0 9 M - 1 s - 1 , E a / R = 1200 (±300) K) and methylglyoxal ( k 298 K = 0.53 ( ± 0.04 ) × 1 0 9 M - 1 s - 1 , E a / R = 1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.
Keywords: Relative kinetics; Photo-oxidations; Structure–activity relationship; Tropospheric lifetime;

This work describes the results of research into a source-oriented pollen concentration forecasting technique. Tests were conducted using the National Center for Atmospheric Research/ Penn State Fifth Generation Mesoscale Model (MM5), the National Oceanographic and Atmospheric Administration (NOAA) Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT_4) Model combined with the locations of oak trees and their aerial coverage from biogenic emissions land cover database version 3.1 (BELD3). Daily forecasts of pollen concentrations via MM5 and HYSPLIT_4 were made with 30-min increments and tested against 30-min oak pollen data collected by the St. Louis County Department of Health in Clayton, Missouri, for the month of April 2000.Results from these tests show that the combination of MM5 and HYSPLIT_4 with accurate source locations can provide short-term forecasts as indicated by the levels of forecast pollen and actual oak pollen levels, which follow similar profiles for the day. From the 30 individual pollen concentration forecasts, two example forecasts are presented. Additional studies need to be conducted to further validate these results, using an array of pollen collectors. A better understanding of the biology of pollen release is critical to improving these pollen concentration forecasts.
Keywords: Mesoscale; Meteorology; Pollen concentrations forecasting;

Analysis of particle-associated semi-volatile aromatic and aliphatic hydrocarbons in urban particulate matter on a daily basis by Jürgen Schnelle-Kreis; Martin Sklorz; Anette Peters; Josef Cyrys; Ralf Zimmermann (7702-7714).
PM2.5 Particle-associated semi-volatile organic compounds (SVOC) were determined in the city of Augsburg, Germany. Daily samples were collected at a central monitoring station from late summer to late autumn 2002. The concentrations of polycyclic aromatic hydrocarbons (PAH), oxidized PAH (O-PAH), n-alkanes, hopanes and long chain linear alkylbenzenes were determined by direct thermal desorption-gas chromatography-time of flight mass spectrometry (DTD-GC-TOFMS). Additionally, PM2.5 particle mass and number concentrations were measured. The sampling campaign can be divided into two parts, distinguished by a lower temperature level in the second part of the campaign. The particulate mass concentration showed no significant changes, whereas most of the SVOC had significant higher mean and peak concentrations in the colder period. The analysis of the data showed an increased influence of non-traffic sources in the colder period, reflected by a weak shift in the PAH profile and a significant shift in the hopane pattern. Statistical analysis of the inter-group correlations was carried out. Eight clusters partly representing different sources of the aerosol have been identified.
Keywords: PM2.5; DTD-GC-TOFMS; PAH; Oxidized PAH; Hopanes; Linear alkylbenzenes;

Gas-phase ozonolysis of the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral by Fabíola Maria N. Nunes; M.C.C. Veloso; P.A. de P. Pereira; J.B. de Andrade (7715-7730).
Biogenic emissions of volatile organic compounds (VOCs) play a fundamental role in atmospheric chemistry. Vegetation is the most abundant natural source of VOCs, while terpenoids, as limonene, α and β pinene and mircene, top the plants emission list. Much interest has been demonstrated in oxidation and photooxidation reactions of VOCs, particularly of monoterpenoids, owing to their diversity and to uncertainties regarding their mechanism of reaction. Quantification of primary carbonylic compounds, as well as of biradical reaction components, is highly relevant to the understanding of the major reactions. In this context, taking into account both structural factors and the fact that these compounds are found in the essential oils of plants typically found in Brazil and that they may be present in the atmosphere from emission by the plants, the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral (a mixture of the isomers geranial and neral) were selected for this study.The ozonolysis reactions of the monoterpenoids were carried out under dark conditions for all experiments, due to their photochemical reactivity. The analysis of the results lets us propose a mechanism by which these reactions occur. The observed results of the ozonolysis of S and R carvone suggest that the stereochemistry of asymmetric carbon does not affect either in the yields of both formaldehyde and of OH radicals produced in the reaction, or in the reactivity of these compounds, for which the rate constants were in the scale of 10−6  s−1.We found that, in the (−)-carveol's cis and trans mixture, even though the hydroxyl in the axial position—in the case of trans-(C) and cis-(D′) isomers—favors the attack by the ozone molecule on the external double bond, thus increasing the mixture's reactivity ( k = 2.0 × 1 0 - 4 s - 1 ) , it affects the average production of formaldehyde. The presence of geraniol and citral led to the production of formaldehyde, propanone, glyoxal, methyl–glyoxal and cyclohexanone (OH radicals) as reaction products. The influence of an electron attractor group bonded to the carbon of the double bond, on the reactivity of the double bond, could not be observed in the case of citral, due to strong interference occurring in the instrument in all experiments with this monoterpenoid. For this reason, only the kinetics of geraniol was monitored ( k = 9.0 × 1 0 - 4 s - 1 ) .
Keywords: Monoterpenoids; Ozone; Gas-phase ozonolysis;

The biogenic species α-pinene, β-pinene, and d-limonene are among the most abundant monoterpenes emitted globally. They are also important precursors to secondary organic aerosol (SOA) formation in the atmosphere. This study involves the development of proposed oxidation mechanisms for these three species. Semi- and non-volatile oxidation products with the potential to lead to SOA formation are predicted explicitly. Simulation code that describes the gas-phase oxidation mechanisms including reactions that lead to ozone (O3) formation is coupled to an equilibrium absorptive partitioning code. The coupled model is used to simulate both gas-phase chemistry and SOA formation associated with oxidation of these three species in chamber experiments involving single as well as multiple oxidants. For the partitioning model, required molecular properties of the oxidation products are taken from the literature or estimated based on structural characteristics. The predicted O3 and SOA concentrations are typically within ±50% of measured values for most of the experiments except for the experiments with low initial hydrocarbon concentrations and the nitrate radical experiments with α-pinene. The developed model will be used to update a gas-phase chemical mechanism and a SOA formation module used in a three-dimensional air quality model.
Keywords: Environmental chamber modeling; d-limonene; Ozone; α-pinene; β-pinene; Secondary organic aerosol;

Assessment of contribution of SO2 and NO2 from different sources in Jamshedpur region, India by A.D. Bhanarkar; S.K. Goyal; R. Sivacoumar; C.V. Chalapati Rao (7745-7760).
Contribution of pollution from different types of sources in Jamshedpur, the steel city of India, has been estimated in winter 1993 using two approaches in order to delineate and prioritize air quality management strategies for the development of region in an environmental friendly manner. The first approach mainly aims at preparation of a comprehensive emission inventory and estimation of spatial distribution of pollution loads in terms of SO2 and NO2 from different types of industrial, domestic and vehicular sources in the region. The results indicate that industrial sources account for 77% and 68% of the total emissions of SO2 and NO2, respectively, in the region, whereas vehicular emissions contributed to about 28% of the total NO2 emissions. In the second approach, contribution of these sources to ambient air quality levels to which the people are exposed to, was assessed through air pollution dispersion modelling. Ambient concentration levels of SO2 and NO2 have been predicted in winter season using the ISCST3 model. The analysis indicates that emissions from industrial sources are responsible for more than 50% of the total SO2 and NO2 concentration levels. Vehicular activities contributed to about 40% of NO2 pollution and domestic fuel combustion contributed to about 38% of SO2 pollution. Predicted 24-h concentrations were compared with measured concentrations at 11 ambient air monitoring stations and good agreement was noted between the two values. In-depth zone-wise analysis of the above indicates that for effective air quality management, industrial source emissions should be given highest priority, followed by vehicular and domestic sources in Jamshedpur region.
Keywords: Air quality management; Air quality modelling; Emission sources and inventory; ISCST; Source contribution; Statistical analysis;

Seasonal variation of indoor radon in dwellings of Malwa region, Punjab by Surinder Singh; Rohit Mehra; Kulwant Singh (7761-7767).
Indoor radon measurements in 105 dwellings belonging to 21 villages of Muktsar and Ferozepur districts of Malwa region, Punjab, have been carried out, using LR-115 type II cellulose nitrate films in the bare mode. The annual average indoor radon value in the study area varies from 76.25 to 145.50 Bq m−3, which is well within the recommended action level [ICRP, 1993. Protection against radon at home and work. Annals of ICRP, ICRP Publication, p. 65]. Seasonal variation of indoor radon shows high values in winter and low values in summer. The winter/summer ratio of radon concentration has been computed for all 105 dwellings. The winter/summer ratio of indoor radon ranges from 0.84 to 1.89 with an average of 1.46. The indoor radon values obtained in the present investigation are more than the world average of 40 Bq m−3
Keywords: Radon; Thoron; Cancer; Dwellings; LR-115;

A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation by William P.L. Carter; David R. Cocker; Dennis R. Fitz; Irina L. Malkina; Kurt Bumiller; Claudia G. Sauer; John T. Pisano; Charles Bufalino; Chen Song (7768-7788).
A new state-of-the-art indoor environmental chamber facility for the study of atmospheric processes leading to the formation of ozone and secondary organic aerosol (SOA) has been constructed and characterized. The chamber is designed for atmospheric chemical mechanism evaluation at low reactant concentrations under well-controlled environmental conditions. It consists of two collapsible 90 m3 FEP Teflon film reactors on pressure-controlled moveable frameworks inside a temperature-controlled enclosure flushed with purified air. Solar radiation is simulated with either a 200 kW Argon arc lamp or multiple blacklamps. Results of initial characterization experiments, all carried out at ∼300–305 K under dry conditions, concerning NO x and formaldehyde offgasing, radical sources, particle loss rates, and background PM formation are described. Results of initial single organic–NO x and simplified ambient surrogate–NO x experiments to demonstrate the utility of the facility for mechanism evaluation under low NO x conditions are summarized and compared with the predictions of the SAPRC-99 chemical mechanism. Overall, the results of the initial characterization and evaluation indicate that this new environmental chamber can provide high quality mechanism evaluation data for experiments with NO x levels as low as ∼2 ppb, though the results indicate some problems with the gas-phase mechanism that need further study. Initial evaluation experiments for SOA formation, also carried out under dry conditions, indicate that the chamber can provide high quality secondary aerosol formation data at relatively low hydrocarbon concentrations.
Keywords: Environmental chambers; Chamber characterization; Atmospheric chemical mechanism evaluation; Ozone; PM formation; Secondary organic aerosol; Oxides of nitrogen; SAPRC-99 mechanism;

Anthropogenic mercury emissions in China by David G. Streets; Jiming Hao; Ye Wu; Jingkun Jiang; Melissa Chan; Hezhong Tian; Xinbin Feng (7789-7806).
An inventory of mercury emissions from anthropogenic activities in China is compiled for the year 1999 from official statistical data. We estimate that China's emissions were 536 (±236) t of total mercury. This value includes open biomass burning, but does not include natural sources or re-emission of previously deposited mercury. Approximately 45% of the Hg comes from non-ferrous metals smelting, 38% from coal combustion, and 17% from miscellaneous activities, of which battery and fluorescent lamp production and cement production are the largest. Emissions are heaviest in Liaoning and Guangdong Provinces, where extensive smelting occurs, and in Guizhou Province, where there is much small-scale combustion of high-Hg coal without emission control devices. Emissions are gridded at 30×30 min spatial resolution. We estimate that 56% of the Hg in China is released as Hg0, 32% as Hg2+, and 12% as Hgp. Particulate mercury emissions are high in China due to heavy burning of coal in residential and small industrial settings without PM controls. Emissions of Hg2+ from coal-fired power plants are high due to the absence of flue-gas desulfurization units, which tend to dissolve the soluble divalent mercury. Metals smelting operations favor the production of elemental mercury. Much of the Hg is released from small-scale activities in rather remote areas, and therefore the activity levels are quite uncertain. Also, emissions test data for Chinese sources are lacking, causing uncertainties in Hg emission factors and removal efficiencies. Overall, we calculate an uncertainty level of ±44% (95% confidence interval) in the estimate of total emissions. We recommend field testing of coal combustors and smelters in China to improve the accuracy of these estimates.
Keywords: Speciated mercury; Emission inventory; Coal combustion; Metals smelting; China;

Effects of soiling and cleaning on the reflectance and solar heat gain of a light-colored roofing membrane by Ronnen Levinson; Paul Berdahl; Asmeret Asefaw Berhe; Hashem Akbari (7807-7824).
A roof with high solar reflectance and high thermal emittance (e.g., a white roof) stays cool in the sun, reducing cooling power demand in a conditioned building and increasing summertime comfort in an unconditioned building. The high initial solar reflectance of a white membrane roof (circa 0.8) can be lowered by deposition of soot, dust, and/or biomass (e.g., fungi or algae) to about 0.6; degraded solar reflectances range from 0.3 to 0.8, depending on exposure. We investigate the effects of soiling and cleaning on the solar spectral reflectances and solar absorptances of 15 initially white or light-gray polyvinyl chloride membrane samples taken from roofs across the United States. Black carbon and organic carbon were the two identifiable strongly absorbing contaminants on the membranes. Wiping was effective at removing black carbon, and less so at removing organic carbon. Rinsing and/or washing removed nearly all of the remaining soil layer, with the exception of (a) thin layers of organic carbon and (b) isolated dark spots of biomass. Bleach was required to clear these last two features. At the most soiled location on each membrane, the ratio of solar reflectance to unsoiled solar reflectance (a measure of cleanliness) ranged from 0.41 to 0.89 for the soiled samples; 0.53 to 0.95 for the wiped samples; 0.74 to 0.98 for the rinsed samples; 0.79 to 1.00 for the washed samples; and 0.94 to 1.02 for the bleached samples. However, the influences of membrane soiling and cleaning on roof heat gain are better gauged by fractional variations in solar absorptance. Solar absorptance ratios (indicating solar heat gain relative to that of an unsoiled membrane) ranged from 1.4 to 3.5 for the soiled samples; 1.1 to 3.1 for the wiped samples; 1.0 to 2.0 for the rinsed samples; 1.0 to 1.9 for the washed samples; and 0.9 to 1.3 for the bleached samples.
Keywords: Roofing; Single-ply membrane; Polyvinyl chloride (PVC); Black carbon; Organic carbon; Biomass; Fungi; Algae; Solar spectral reflectance; Solar reflectance; Solar absorptance; Absorption; Optical depth; Soiling; Cleaning; Wiping; Washing; Rinsing; Bleaching;

A gas particle partitioner (GPP, US patent 6,761,752 B2) that allows highly efficient separation of gas and particles with no effect on the thermodynamic conditions and substantially no change of the composition of the gas has been developed. The GPP is a coaxial arrangement with inner and outer electrode. It utilizes a corona discharge to electrically charge the particles and a strong electric field in a separate unit to take them out of the sample flow. Several measures were taken to minimize an effect of the corona discharge on the gas composition. The GPP is designed such that when switched on, the sample flow is particle free, whereas when switched off, the sample flow contains a representative sample of the aerosol.The GPP as described in this manuscript was designed to meet the requirements for precise artifact correction with particle mass concentration monitors, such as the TEOM. This paper focuses on the gas particle separation efficiency of the instrument. The separation efficiency was determined for both, (ultra-) fine and coarse particles. The (ultra-) fine particles were generated with diameters ranging from 18 to 255 nm of polystyrene latex particles and their size distributions measured with a scanning mobility particle sizer (SMPS). Coarse particles with diameters between 4.5  and 10.7 μm were generated from a sodium chloride solution and characterized with an aerodynamic particle sizer (APS) and a tapered element oscillating microbalance (TEOM). The investigations showed that the separation efficiency was very near 100% for all particles with diameters larger than 25 nm, whereas it decreased for smaller diameters. Particles of size 18 nm were separated from the gas flow with an efficiency of approximately 97%. Along with near 100% separation efficiency, the additional gas concentrations were 42 ppbV for O3 and 15 ppbV for NO2.
Keywords: Airborne particles; TEOM; Artifact correction; Electrostatic separation; Corona; PM sampling;

Effect of fuel composition and engine operating conditions on polycyclic aromatic hydrocarbon emissions from a fleet of heavy-duty diesel buses by McKenzie C.H. Lim; Godwin A. Ayoko; Lidia Morawska; Zoran D. Ristovski; E. Rohan Jayaratne (7836-7848).
Emissions from 12 in-service heavy-duty buses powered by low- (LSD) and ultra low-sulfur (ULSD) diesel fuels were measured with the aim to characterize the profile of polycyclic aromatic hydrocarbons (PAHs) in the exhaust and to identify the effect of different types of fuels on the emissions. To mimic on-road conditions as much as possible, sampling was conducted on a chassis dynamometer at four driving modes, namely: mode 7 or idle (0% power), mode 11 (25% power), mode 10 (50% power) and mode 8 (100% power). Irrespective of the type of fuel used, naphthalene, acenaphthene, acenaphthylene, anthracene, phenanthrene, fluorene, fluoranthene and pyrene were found to be the dominant PAHs in the exhaust emissions of the buses. However, the PAH composition in the exhausts of ULSD buses were up to 91±6% less than those in the LSD buses. In particular, three- and four-ringed PAHs were more abundant in the later than in the former. Lowering of fuel sulfur content not only reduced PAH emission, but also decreased the benzo(a)pyrene equivalent (BAPeq) and hence the toxicity of the exhaust. Result from multicriteria decision-making and multivariate data analysis techniques showed that the use of ULSD afforded cleaner exhaust compositions and emissions with characteristics that are distinct from those obtained by the use of LSD.
Keywords: Diesel buses; Sulfur; PAH emissions; Toxicity evaluation and multivariate analysis;

Results from a pilot-scale air quality study in Addis Ababa, Ethiopia by V. Etyemezian; M. Tesfaye; A. Yimer; J.C. Chow; D. Mesfin; T. Nega; G. Nikolich; J.G. Watson; M. Wondmagegn (7849-7860).
Twenty-one samples were collected during the dry season (26 January–28 February 2004) at 12 sites in and around Addis Ababa, Ethiopia and analyzed for particulate matter with aerodynamic diameter <10 μm (PM10) mass and composition. Teflon-membrane filters were analyzed for PM10 mass and concentrations of 40 elements. Quartz-fiber filters were analyzed for chloride, sulfate, nitrate, and ammonium ions as well as elemental carbon (EC) and organic carbon (OC) content. Measured 24-h PM10 mass concentrations were <100 and 40 μg m−3 at urban and suburban sites, respectively. PM10 lead concentrations were <0.1 μg m−3 for all samples collected, an important finding because the government of Ethiopia had stopped the distribution of leaded gasoline a few months prior to this study. Mass concentrations reconstructed from chemical composition indicated that 34–66% of the PM10 mass was due to geologically derived material, probably owing to the widespread presence of unpaved roads and road shoulders. At urban sites, EC and OC compounds contributed between 31% and 60% of the measured PM10 while at suburban sites carbon compounds contributed between 24% and 26%. Secondary sulfate aerosols were responsible for <10% of the reconstructed mass in urban areas but as much as 15% in suburban sites, where PM10 mass concentrations were lower. Non-volatile particulate nitrate, a lower limit for atmospheric nitrate, constituted <5% and 7% of PM10 at the urban and suburban sites, respectively. At seven of the 12 sites, real-time PM10 mass, real-time carbon monoxide (CO), and instantaneous ozone (O3) concentrations were measured with portable nephelometers, electrochemical analyzers, and indicator test sticks, respectively. Both PM10 and CO concentrations exhibited daily maxima around 7:00 and secondary peaks in the late afternoon and evening, suggesting that those pollutants were emitted during periods associated with motor-vehicle traffic, food preparation, and heating of homes. The morning concentration maxima were likely accentuated by stable atmospheric conditions associated with overnight surface temperature inversions. Ozone concentrations were measured near mid-day on filter sample collection days and were in all cases <45 parts per billion.
Keywords: PM10; Africa; Lead; Carbon monoxide; Ethiopia;

Carbonaceous aerosol emissions from India by D.C. Parashar; Ranu Gadi; T.K. Mandal; A.P. Mitra (7861-7871).
Budget estimate for carbonaceous aerosols including black carbon (BC) and organic carbon, emitted from the combustion of various fuels, is very important for regional climate studies. Emission factors for carbonaceous aerosols from bio-fuels and soft coke were determined in a controlled combustion study. The emission factors thus obtained along with those available for other fossil fuels consumed in different sectors have been applied to assess the budget for carbonaceous aerosols from India. Preliminary calculations give a range of 1.6–1.8 Tg of carbonaceous aerosols that include 0.4–1.4 Tg of BC. A major (∼80%) portion of carbonaceous aerosols emitted from India is found to originate from the use of biomass for energy as 70–80% of energy requirement in rural India is met by combustion of traditional bio-fuels.
Keywords: Carbonaceous aerosols; Organic carbon; Black carbon; Emission factors; Biomass burning; Bio-fuels; Fossil fuels;

The Guttalgor method has been used to determine the chemical species concentrations in size-selected raindrops in nine rain events at Hong Kong from 1999 to 2001. The curve (concentration against raindrop radius) patterns for all the species are similar but depend on the starting time of sampling within a rain event. In these plots, the maximum concentration occurs at the same range of droplet radius, irrespective of the species, and this indicates the importance of coalescence and breakup processes. The maximum is located at a smaller droplet radius than was found in previous studies in Germany. All results show almost constant concentrations with size for large raindrops, and these indicate the in-cloud contributions. The pH of raindrops of similar size is linearly correlated with a function of the sulfate, nitrate, acetate, formate, calcium and ammonium ion species concentrations. Within a single raindrop, chloride depletion is not significant, and sulfate, ammonium and hydrogen ions are found in ratios compatible with the precursor solid-phase mixture of ammonium sulfate and ammonium bisulphate. When simulated by a below-cloud model, good agreement between the modeled and measured sodium and sulfate concentrations has been found. Below-cloud sulfur dioxide scavenging contributes at most 60% of the sulfate concentration in a single raindrop.
Keywords: Guttalgor; Concentration and radius; Below-cloud; scavenging;

Experimental and numerical study of the dispersion of motor vehicle pollutants under idle condition by Z. Ning; C.S. Cheung; Y. Lu; M.A. Liu; W.T. Hung (7880-7893).
The aim of the work presented here is to study experimentally and numerically the dispersion characteristics of vehicular exhaust plume at an idle condition in an idealized and simplified environment. The gaseous and particulate concentrations in the exhaust plume of three idling motor vehicles were measured in an isolated environment under calm weather conditions. Despite the difference in the initial concentrations, the pollutants decayed exponentially in all directions.The CFD code PHOENICS 3.3, with the k–ε eddy dissipation sub-model, was used for the numerical simulation. The simulated results match very well with the experimental results close to the source of emission but decay to the ambient concentrations much slower. The effects of the initial emission concentration, exit velocity, exit direction and crosswind intensity have been investigated parametrically. The initial pollutant concentration will increase the local concentrations but the pattern of dispersion remains the same. The exit velocity will increase the momentum of the jet, resulting in a deeper penetration downstream. The exit angle has a stronger influence on pollutant dispersion than both initial pollutant concentration and exit velocity. When the exit angle is 15°, the pollutants tend to spread on the ground region. Crosswind shows a significant effect on the dispersion of the exhaust plume also. It will divert the plume to disperse in the same direction of the wind with limited penetration in the downstream direction.
Keywords: Exhaust plume; Dispersion; Concentration; Pollutant; Idle condition;

Concentrations and trends of benzene in ambient air over New York State during 1990–2003 by Nenad Aleksic; Garry Boynton; Gopal Sistla; Jacqueline Perry (7894-7905).
Since 1990s, a systematic program to measure air toxics has been active in New York State with monitors located both in urban and rural areas. In this study we examined the spatial and temporal characteristics of benzene, a known human carcinogen that is emitted by many source categories. The analysis indicates that ambient concentration levels of benzene have decreased by as much as 60% over this period not only in the ozone non-attainment area of New York City that had the reformulated gas (RFG) requirements, but also over the rest of the state as well. Although the rate of decrease appears to have flattened out in recent years, the annual average concentration levels are found to be above the health risk threshold even at the remote location, Whiteface Mountain, suggesting the need for further reductions in benzene emissions.
Keywords: Air toxics; Benzene measurements; New York State; Spatial and temporal concentrations and trends;

Dicarboxylic acid concentration trends and sampling artifacts by Joshua Ray; Stephen R. McDow (7906-7919).
Dicarboxylic acids associated with airborne particulate matter were measured during a summer period in Philadelphia that included multiple air pollution episodes. Samples were collected for two 10 h periods each day using a high-volume sampler with two quartz fiber filters in series, and analyzed by gas chromatography mass spectrometry (GCMS) with diazomethane derivatization. Among the dicarboxylic acids investigated, phthalic acid and adipic acid exhibited the greatest diurnal variations and the strongest linear relationship with maximum daily ozone concentration. Dicarboxylic acids and ozone concentration exhibited a poor linear relationship with organic to elemental carbon ratio. All species investigated were affected by significant sampling artifact errors at low concentrations, but sampling errors were negligible at high concentrations observed during ozone episodes.
Keywords: Dicarboxylic acids; Secondary organic aerosol; Sampling artifacts;