Roadside aerosol study using hygroscopic,organic and volatility TDMAs: Characterization and mixing state

Traffic-related aerosol particles are ubiquitous in the urban atmosphere. As they are produced at ground level, they can also cause adverse health effects to urban dwellers. However, knowledge of the formation, transformation and chemically resolved size distribution of urban ultrafine particles is incomplete. Thus, more of these measurements are needed for better assessment of ambient air quality and its potential health effects. The particle number concentration, aerosol black carbon (BC) concentration and size distribution of traffic-related aerosols were measured near two major roads in Kuopio, Finland, from 16 June to 5 July, 2004. Furthermore, the properties of roadside aerosol particles were examined with the Tandem Differential Mobility Analyzer technique (TDMA). A suite of TDMA instruments relying on water (hygroscopic TDMA) and ethanol (organic TDMA) condensation as well as heating (volatility TDMA) were deployed to study the composition of the nucleation and Aitken mode particles (D_p = 10–50 nm) formed from vehicle exhaust. The results show that a simple three-component model was able to reproduce characteristic insoluble, organic and water-soluble volume fractions. Insoluble constituents were dominant in the Aitken mode particles, whereas organic compounds dominated the nucleation mode sizes. On average, only a small volume fraction was water-soluble, but a clear external mixing was observed particularly when enough time was allowed after the tail pipe emissions. The contribution of the insoluble material was seen to increase as a function of particle size, being typically less than 10% at 10 nm and between 20 and 50% at 50 nm, in contrast to the organic fraction, which decreased from about 80% at nucleation mode size range to 50–60% at 50 nm.     

Measurements of the physical properties of particles in the urban atmosphere

Measurements of the physical properties of particles in the atmosphere of a UK urban area have been made, including particle number count by condensation nucleus counters with different lower particle size cut-offs; particle size distributions using a Scanning Mobility Particle Sizer; total particle Fuchs surface area using an epiphaniometer and particle mass using Tapered Element Oscillating Micro-balance (TEOM) instruments with size selective (PM₁₀ and PM_2.5) inlets. Mean particle number counts at three sites range from 2.86×10⁴ to 9.60×10⁴ cm^-3. A traffic-influenced location showed a substantially higher ratio of particle number to PM₁₀ mass than a nearby background location despite being some 70 m from the roadway. Operating two condensation nucleus counters in tandem to determine particles in the 3–7 nm size range by difference showed signficant numbers of particles in this range, apparently related to homogeneous nucleation processes. Measurements with the Scanning Mobility Particle Sizer showed a clear difference between roadside size distributions and those at a nearby background location with an additional mode in the roadside samples below 10 nm diameter. Particle number counts were found to show a significant linear correlation with PM₁₀ mass (r²=0.44; n=44 for 24 h data at an urban background location), although during one period of high pollution a curvilinear relationship was found. Measurements of the diurnal variation in PM₁₀ mass, particle number count and Fuchs surface area show the same general pattern of behaviour of the three variables, explicable in terms of vehicle emission source strength and atmospheric dispersion, although the surface area growth was out of phase with the particle number and mass. It appears that particle number gives the clearest indication of recent road traffic emissions.     

Dilution and aerosol dynamics within a diesel car exhaust plume—CFD simulations of on-road measurement conditions

Vehicle particle emissions are studied extensively because of their health effects, contribution to ambient PM levels and possible impact on climate. The aim of this work was to obtain a better understanding of secondary particle formation and growth in a diluting vehicle exhaust plume using 3-d information of simulations together with measurements. Detailed coupled computational fluid dynamics (CFD) and aerosol dynamics simulations have been conducted for H₂SO₄–H₂O and soot particles based on measurements within a vehicle exhaust plume under real conditions on public roads.Turbulent diffusion of soot and nucleation particles is responsible for the measured decrease of number concentrations within the diesel car exhaust plume and decreases coagulation rates. Particle size distribution measurements at 0.45 and 0.9 m distance to the tailpipe indicate a consistent soot mode (particle diameter D_p∼50 nm) at variable operating conditions. Soot mode number concentrations reached up to 10¹³ m⁻³ depending on operating conditions and mixing.For nucleation particles the simulations showed a strong sensitivity to the spatial dilution pattern, related cooling and exhaust H₂SO_4(g). The highest simulated nucleation rates were about 0.05–0.1 m from the axis of the plume. The simulated particle number concentration pattern is in approximate accordance with measured concentrations, along the jet centreline and 0.45 and 0.9 m from the tailpipe. Although the test car was run with ultralow sulphur fuel, high nucleation particle (D_p⩽15 nm) concentrations (>10¹³ m⁻³) were measured under driving conditions of strong acceleration or the combination of high vehicle speed (>140 km h⁻¹) and high engine rotational speed (>3800 revolutions per minute (rpm)).Strong mixing and cooling caused rapid nucleation immediately behind the tailpipe, so that the highest particle number concentrations were recorded at a distance, x=0.45 m behind the tailpipe. The simulated growth of H₂SO₄–H₂O nucleation particles was unrealistically low compared with measurements. The possible role of low and semi-volatile organic components on the growth processes is discussed. Simulations for simplified H₂SO₄–H₂O–octane–gasoil aerosol resulted in sufficient growth of nucleation particles.     

A review of particle formation events and growth in the atmosphere in the various environments and discussion of mechanistic implications

This review highlights recent observations from a large number of studies investigating formation and growth within different environments and discusses the importance of various mechanisms of particle formation and growth between the different environments. Whilst, several mechanisms for new particle formation which proposed the importance of each mechanism are still the centre of much debate. Proposed nucleation mechanisms include condensation of a binary mixture of sulphuric acid and water; ternary nucleation of sulphuric acid, water and a third molecule, most likely ammonia; ion-induced nucleation; secondary organic aerosol formation involving condensation of low- or non-volatile organic compounds and homogeneous nucleation of iodine oxides. Laboratory and modelling studies have shown these mechanisms can occur in the atmosphere although the contribution depends on the concentrations of precursor compounds present. In addition, atmospheric particle formation events are significantly affected by environmental factors, such as temperature, humidity and the surface area of pre-existing particles, which is also discussed here. One major problem hampering our current understanding is that these new particles are smaller than the lower size detection limit of most instruments and are only observed after some particle growth has occurred.Particles growth occurs through condensation of supersaturated vapours on the surface of the nucleated particles. This requires a lower degree of supersaturation than nucleation and thus condensation of the nucleating species reduces the rate of particle formation. Therefore, it is believed that particle growth often occurs through the condensation of other gases, including organic and inorganic compounds, than those responsible for nucleation. This decoupling of nucleation and growth means that the individual gases responsible for nucleation and growth can be unclear.Since observations of particle formation only occur following growth to observable sizes it is possible that a pool of undetectable particles exist at all times but are only observed following significant condensational growth.     

The effects of aging processes on critical supersaturation ratios of ultrafine carbon aerosols

The condensation properties of polydisperse aged ultrafine carbon aerosols (particle diameter<1 μm) have been investigated by means of a variable supersaturation condensation nucleus counter. The critical supersaturation (S_c), as the point, where 50% of all particles have been activated and grew to droplets was compared to the median dry particle diameter for pure carbon aerosols, benzo[a]pyrene-tagged carbon aerosols and external mixtures of the carbon particles with sodium chloride and sulphuric acid aerosols. Additionally, ozone as oxidising gaseous compound was added in some of the experiments. Simple coagulation of pure and benzo[a]pyrene-tagged carbon particles resulted in only slightly lower values for S_c due to the increased median particle diameter. The formation of soluble functionalities on the particle surface, i.e. the coagulation with the soluble sodium chloride and sulphuric acid aerosols or the chemical decomposition of benzo[a]pyrene into polar, hydrophilic products due to the reaction with ozone resulted in significant lower values for S_c for the modified carbon aerosol. The necessary supersaturations for the increased hydrophilic particles dropped to atmospherically relevant values of 3% after 5 h reaction time (benzo[a]pyrene decomposition) and 15 h (coagulation with soluble particles), respectively.     

Assessment of the aerosol water content in urban atmospheric particles by the hygroscopic growth measurements in Sapporo,Japan

Aerosol water content (AWC) of urban atmospheric particles was investigated based on the hygroscopic growth measurements for 100 and 200 nm particles using a hygroscopicity tandem differential mobility analyzer in Sapporo, Japan in July 2006. In most of the humidogram measurements, presence of less and more hygroscopic mode was evident from the different dependence on relative humidity (RH). The volume of liquid water normalized by that of dry particle (V_w(RH)/V_dry) was estimated from the HTDMA data for 100 and 200 nm particles. The RH dependence of V_w(RH)/V_dry was well represented by a fitted curve with a hygroscopicity parameter κ_eff. The κ_eff values for 200 nm particles were in general higher than those for 100 nm particles, indicating a higher hygroscopicity of 200 nm particles. Based on the κ_eff values, the volume mixing ratios of water-soluble inorganic compounds (ammonium sulfate equivalent) were estimated to be on average 31% and 45% for 100 and 200 nm particles, respectively. The diurnal variation of κ_eff, with relatively higher values in the noontime and nighttime and lower values in the morning and evening hours, was observed for both particle sizes. The V_w(RH)/V_dry values under ambient RH conditions were estimated from κ_eff to range from 0.05 to 2.32 and 0.06 to 2.43 for 100 nm and 200 nm particles, respectively. The degree of correlation between κ_eff and V_w(RH)/V_dry at ambient RH suggests a significant contribution of the variation of κ_eff to atmospheric AWC in Sapporo.     

Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

The effect of humidity and state of water surfaces on deposition of aerosol particles onto a water surface

Deposition processes of particles with dry diameter larger than about 10 μm are dominated by gravitational settling, while molecular diffusion and Brownian motion predominate the deposition processes of particles smaller than 0.1 μm in dry diameter. Many air pollution derived elements exhibit characteristics common to sub-micron particles. The objective of the present study is to examine the effects of meteorological conditions within the turbulent transfer layer on the deposition velocity of particles with dry diameter between 0.1 and 1 μm. It is for these sub-micron particles that particle growth by condensation in the deposition layer, the broken water surface effect and the enhanced transfer process due to atmospheric turbulence in the turbulent transfer layer play important roles in controlling the particle deposition velocity. Results of the present study show that the `dry air’ assumption of Williams’ model is unrealistic. Effects of ambient air relative humidity and water surface temperature cannot be ignored in determining the deposition velocity over a water surface. Neglecting effects of ambient air relative humidity and water surface temperature will result in defining atmospheric stability incorrectly. It is found that the largest effect of air relative humidity on deposition velocity occurs at an air–water temperature difference corresponding to the point of `displaced neutral stability'. For a given wind speed of U=5 m s⁻¹ the additive effects of water surface temperature, T_w, changes from 5 to 25°C and ambient air relative humidity variations from 85 to 60%, respectively, lead to a maximum difference in v_d of about 20%. For a higher wind speed of 10 m s⁻¹, however, the corresponding change in v_d reduces to less than 5%. This is further confirmation that wind speed is one of the strongest variables that governs the magnitude of v_d. The present study also found that the broken surface transfer coefficient, k_bs, given as a multiple of the smooth surface transfer coefficient, k_ss, is physically more meaningful than assigning it a constant value independent of particle size. The method used in this study requires only a single level of atmospheric data coupled with the surface temperature measurement. The present method is applicable for determining deposition velocity not only at the conventional measurement height of 10 m but also at any other heights that are different from the measurement height.     

Characterisation of single particles from in-port ship emissions

Emissions from shipping traffic may impact severely upon air quality in port cities. In this study, the size and composition of freshly emitted individual ship exhaust particles has been investigated using an aerosol time-of-flight mass spectrometer (ATOFMS) co-located with a suite of real-time instrumentation at a site in the Port of Cork, Ireland. The collected spectra were clustered using the K-means algorithm and a unique ship exhaust class containing internally mixed elemental and organic carbon, sodium, calcium, iron, vanadium, nickel and sulfate was identified. Over twenty sharp emission events were observed for this particle type during the three week measurement period in August 2008. Coincident increases in mass concentrations of sulfate, elemental carbon and particles below 2.5 μm in diameter (PM_2.5) were also observed during these events. Simultaneous scanning mobility particle sizer (SMPS) measurements indicate that the vast majority of freshly emitted ship exhaust particles lie in the ultrafine mode (<100 nm diameter). A second particle class consisted of internally mixed organic carbon, elemental carbon, ammonium and sulfate, and is tentatively attributed to aged or regionally transported ship exhaust. The results suggest that ATOFMS single particle mass spectra, when used in conjunction with other air quality monitoring instrumentation, may be useful in determining the contribution of local shipping traffic to air quality in port cities.     

Aerosol formation yields from the reaction of catechol with ozone

The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm^?3. Analysis of the data clearly shows that Y is a strong function of M_o and that secondary organic aerosol formation can be expressed by a one-product gas–particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.     

Characterization of aging wood chip combustion aerosol in an environmental chamber

Aging of aerosol from wood chip combustion in a stoker burner was monitored in an outdoor environmental chamber for 19–27 h in order to study the size, volatility and organic carbon (OC) content of the combustion aerosol particles during aging. A scanning mobility particle sizer, a volatility tandem differential mobility analyzer (VTDMA), and a thermal–optical carbon analyzer were utilized. The VTDMA and carbon analyses were performed at the beginning, after 17–24 h of aging and at one intermediate point. The size decrease of freshly emitted particles was 6–10% when heated to $360{}^{\circ }\mathrm{C}$, and was found to depend on the experiment start time. For particles aged for 24 h, a 74–86% decrease in particle size at $360{}^{\circ }\mathrm{C}$ was observed. The more volatile OC fraction and the total OC fraction in the particles increased and the less volatile OC fraction decreased with aging. This suggests that during aging more volatile compounds condense on or heavier compounds photodegrade into lighter ones in the particles. Occasionally, new particle formation and growth were observed in the following day. The new particles were found to be composed mainly of volatile material.     

The effect of water on gas–particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems

An investigation of the effect of relative humidity on aerosol formation from m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. Experiments were performed in the presence and absence of ammonium sulfate seed particles (both aqueous and dry) to ascertain the effect of partitioning of oxidation products into a strong electrolytic solution or onto dry crystalline seed particles. In marked contrast to the α-pinene/ozone system, the final measured secondary organic aerosol yield was unaffected by the presence of gas-phase or liquid-phase water at relative humidities (RH) up to 50%. The hygroscopic nature of the aerosol generated upon photooxidation of m-xylene and 1,3,5-trimethylbenzene was examined; the hygroscopicity of the aerosol at 85% RH for both parent organics increased with the extent of the reaction, indicating that the first-generation oxidation products undergo further oxidation. Limited identification of the gas- and aerosol-phase products of m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. It is evident that a more complete molecular identification of aromatic photooxidation aerosol awaits analytical techniques not yet brought to bear on this problem.     

Mass transfer coefficients for volatilization of polychlorinated biphenyls from the Hudson River,New York measured using micrometeorological approaches

Air–water exchange is an important process controlling the fate of many organic chemicals in the environment. Modeling this process is hampered by the lack of direct observations. Thus, the purpose of this work was to derive direct measurements of the mass transfer coefficients for air–water exchange (v_aw) of polychlorinated biphenyls (PCBs) that may be used to check the validity of values derived from tracer gas experiments. v_aw values for PCBs were determined using previously published turbulent fluxes divided by the corresponding dissolved phase concentrations. The median v_aw values for each homolog decreased with increasing molecular weight and ranged from 0.29 for hexachlorobiphenyls to 2.2 m d^?1 for monochlorobiphenyls with a propagated uncertainty of about 70%, lower than in previous studies. Due to relatively low wind speeds and possible sorption of PCBs to colloids, these numbers may be biased low. These field measurements of v_aw differ by as much as a factor of 23 from predictions based on the widely-used Whitman two-film model. Therefore a new formulation for the calculation of v_aw based on field measurements is needed. This study demonstrates that micrometeorological approaches are a viable option for the measurement of v_aw for hydrophobic organics such as PCBs and should be used to generate enough field data on the air–water exchange of hydrophobic organics to allow the development of new predictive models.     

On-road measurements of ultrafine particle concentration profiles and their size distributions inside the longest highway tunnel in Southeast Asia

This study measured ultrafine particle (UFP) levels and their size distributions in the Hsuehshan tunnel from August 12 to 19, 2009, using a Fast Mobility Particle Sizer. Measurement results demonstrate that traffic volume, the slope of the tunnel (downhill or uphill) and the ventilation system affected UFP levels inside the tunnel. Average UFP levels were about 1.0 × 10⁵–3.0 × 10⁵ particles cm^?3 at normal traffic volume. A traffic jam in the tunnel could raise UFP levels to over 1.0 × 10⁶ particles cm^?3. UFP levels at the uphill bore were significantly higher than those at the downhill bore due to high UFP levels exhausted from vehicles going uphill at high engine load conditions. UFP levels eventually diluted 10–50% with fresh air from tunnel air shafts. Gas-to-particle condensation conversion markedly produced nucleation mode particles at the tunnel entrance section. Observations also showed Aitken mode particles markedly formed by coagulation growth of nucleation mode particles in the tunnel middle section and exit section. That is, the particle size distributions changed significantly inside the tunnel. Measurement results suggest that particles in the Aitken mode in the long tunnel governed UFP levels.     

Generation and growth of aerosols over Pune,India

The measured physical size distributions of sub-micron particles during cold season at Pune, India are analyzed to explore the characteristics of nucleation and growth properties. Preliminary analysis of aerosol size distribution in time-series shows large increase in number concentration due to nucleation events between 0800 h and 1030 h at this location. The observable quantities such as condensable vapor concentration (C), its source rate (Q), growth rate (GR) and condensable sink (CS) are estimated from the time-series evolutions of aerosol size distributions. The concentration of vapor and its source rate were about 19.8 ± 2.15 × 10⁷ molecules cm^?3 and 1.28 ± 0.084 × 10⁷ cm^?3 s^?1 respectively. The average condensation sink and growth rate were 7.1 ± 0.4 × 10^?2 s^?1 and 16.95 ± 1.86 nm h^?1 respectively during the growth period. The values are high enough to trigger the nucleation bursts and enhance subsequent growth rates of nucleation mode particles at this location. The magnitudes are in the range of those observed at New Delhi, India and much higher than those of European cities. The ratio of apparent to real nucleation rate is found to be a measure of number concentration of freshly produced particles by photo-chemical nucleation. The predicted number concentrations corresponding to measured distributions of mid-point diameter increases with the size for both 1 nm nucleated clusters and 3 nm particles. The database of all the possible event days and the event characteristics forms the basis for future works into the causes and implications of atmospheric particle formation at this location.     

Characterization and source presumption of wintertime submicron organic aerosols at Saitama,Japan, using the Aerodyne aerosol mass spectrometer

The chemical composition and size distribution of submicron aerosols were analyzed at a suburban site at Saitama, Japan, in the winter of 2004/2005, using an Aerodyne aerosol mass spectrometer. Although organics and nitrate were the dominant species during the sampling period, a large fraction of sulfate was observed at the accumulation mode when mass loading was low and wind speed was high. The size distributions of m/z 44 (mostly CO₂⁺) and sulfate aerosols during periods of high wind speed showed remarkable similarities in the accumulation mode, indicating that oxygenated organics were aged aerosols and internally mixed with sulfate. Ozone concentrations were also increased during these high wind speed periods although nighttime (e.g., 12/17 2004), indicating that the oxygenated compounds were strongly influenced by transported and aged air masses. The diurnal profiles of ultrafine-mode organics and hydrocarbon-like organic aerosols (HOA) were similar to NO_X derived from traffic and other combustion sources. The temporal variation of oxygenated organic aerosols (OOA) agreed well with that of nitrate as a secondary aerosol tracer, and the diurnal profile of the OOA fraction of organics increased during the day associated with higher UV light intensity. The result of time and size-resolved chemical composition of submicron particles indicated that the OOA is associated with both photochemical activity and transboundary pollution, and ultrafine-mode organic and HOA aerosols are mainly associated with combustion sources.     

Measurement of aerosol number size distributions in the Yangtze River delta in China: Formation and growth of particles under polluted conditions

Particle size distribution is important for understanding the sources and effects of atmospheric aerosols. In this paper we present particle number size distributions (10 nm–10 μm) measured at a suburban site in the fast developing Yangtze River Delta (YRD) region (near Shanghai) in summer 2005. The average number concentrations of ultrafine (10–100 nm) particles were 2–3 times higher than those reported in the urban areas of North America and Europe. The number fraction of the ultrafine particles to total particle count was also 20–30% higher. The sharp increases in ultrafine particle number concentrations were frequently observed in late morning, and the particle bursts on 5 of the 12 nucleation event days can be attributed to the homogeneous nucleation leading to new particle formation. The new particle formation events were characterized with a larger number of nucleation-mode particles, larger particle surface area, and larger condensational sink than usually reported in the literature. These suggest an intense production of sulfuric acid from photo-oxidation of sulfur dioxide in the YRD. Overall, the growth rate of newly formed particles was moderate (6.4 ± 1.6 nm h^?1), which was comparable to that reported in the literature.     

Modelling aerosol number distributions from a vehicle exhaust with an aerosol CFD model

Vehicular traffic contributes significantly to the aerosol number concentrations at the local scale by emitting primary soot particles and forming secondary nucleated nanoparticles. Because of their potential health effects, more attention is paid to the traffic induced aerosol number distributions.The aim of this work is to explain the phenomenology leading to the formation and the evolution of the aerosol number distributions in the vicinity of a vehicle exhaust using numerical modelling. The emissions are representative of those of a light-duty diesel truck without a diesel particle filter. The atmospheric flow is modelled with a computational fluid dynamics (CFD) code to describe the dispersion of pollutants at the local scale. The CFD code, coupled to a modal aerosol model (MAM) describing the aerosol dynamics, is used to model the tailpipe plume of a vehicle with emissions corresponding to urban driving conditions. On the basis of available measurements in Schauer et al. (1999), three surrogate species are chosen to treat the semi-volatile organic compounds in the emissions.The model simulates the formation of the aerosol distribution in the exhaust plume of a vehicle as follows. After emission to the atmosphere, particles are formed by nucleation of sulphuric acid and water vapour depending strongly on the thermodynamic state of the atmosphere and on the dilution conditions. The semi-volatile organic compounds are critical for the rapid growth of nanoparticles through condensation. The semi-volatile organic compounds are also important for the evolution of primary soot particles and can contribute substantially to their chemical composition.The most influential parameters for particle formation are the sulphur fuel content, the semi-volatile organic emissions and also the mass and initial diameter of the soot particles emitted. The model is able to take into account the complex competition between nucleation, condensation and dilution, as well as the interactions among the different aerosol modes. This type of model is a useful tool to better understand the dynamics leading to the formation of traffic induced aerosol distributions. However, some key issues such as the turbulence in the exhaust plume and in the wake of the car, the magnitude and chemical composition of semi-volatile organic emissions and the possible nucleation of organic species need to be investigated further to improve our understanding of ultrafine particle formation.     

Particle volatility in the vicinity of a freeway with heavy-duty diesel traffic

During February–March 2006, a major field sampling campaign was conducted adjacent to the Interstate 710 (I-710) freeway in Los Angeles, CA. I-710 has high traffic volumes (ca. 11,000 vehicles h⁻¹) and a high percentage (17–18%) of heavy-duty diesel vehicle (HDDV) traffic. The volatility of ambient particles of 20, 40, 80 and 120 nm in diameter was investigated using a Tandem Differential Mobility Analyzer (TDMA) at two locations—close to the freeway (10 m) and approximately 150 m downwind. The smallest particles (20 nm) are largely volatile at both locations. Larger particles, e.g., ⩾40 nm) showed evidence of external mixing, with the non-volatile fraction increasing with particle size. Particle volatility increased with decreasing ambient temperature. The HDDVs contribute to relatively larger non-volatile particle number and volume fractions and greater external mixing than earlier observations at a pure light-duty gasoline vehicle freeway [Kuhn et al., 2005c. Atmospheric Environment 39, 7154–7166]. Finally, the fraction of externally mixed soot particles decreased as the downwind distance increased from the I-710, due to atmospheric processes such as vapor adsorption and condensation as well as particle coagulation.     

Source apportionment of urban fine and ultra-fine particle number concentration in a Western Mediterranean city

Extensive measurements on particle number concentration and size distribution (13–800 nm), together with detailed chemical composition of PM_2.5 have constituted the main inputs of the database used for a source apportionment analysis. Data were collected at an urban background site in Barcelona, Western Mediterranean.The source identification analysis helped us to distinguish five emission sources (vehicle exhausts, mineral dust, sea spray, industrial source and fuel-oil combustion) and two atmospheric processes (photochemical induced nucleation and regional/urban background particles derived from coagulation and condensation processes). After that, a multilinear regression analysis was applied in order to quantify the contribution of each factor.This study reveals that vehicle exhausts contribute dominantly to the number concentration in all the particle sizes (52–86%), but especially in the range 30–200 nm. This work also points out the importance of the regional and/or urban formed aerosols (secondary inorganic particles) on the total number concentration (around 25% of the total number), with a higher impact on the accumulation mode. The photo-chemically induced nucleation of aerosols only represents a small proportion of the total number as an annual mean (3%), but is very relevant when considering only the nucleation mode (13–20 nm) fraction (23%). The other sources recognized registered sporadic contributions to the total number, coinciding with specific meteorological scenarios.This study discloses the main sources and features affecting and controlling the fine and ultra-fine aerosols in a typical city in the Western Mediterranean coast. Whereas the road traffic appears to be the most important source of sub-micrometric aerosols, other sources may not be negligible under specific meteorological conditions.