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The study was part of the South American Emissions, Megacities and Climate Project (SAEMC). The objective was to identify and quantify organic and elemental carbon (OC and EC), monosaccharides, polycyclic aromatic hydrocarbons (PAHs), oxy and nitro-PAHs, water-soluble ions (WSI), and elements in particulate matter collected in intensive campaigns during a period (June, 2010) in Sao Paulo (Brazil), Lima (Peru), and Medellin (Colombia). PM10 concentration was higher in Sao Paulo than in the other two sites and 75% of the samples had concentrations above the World Health Organization (WHO) guideline. High concentrations of levoglucosan, a biomass burning tracer, highlighted the importance of this source in the Brazilian megacity. Levoglucosan-to-mannosan ratios for Sao Paulo suggested sugarcane burning, which in 2010 occurred in 70% of the state municipalities during harvest. Vehicular-related elements (Fe and Cu) had higher concentrations in Sao Paulo. As and Pb in Medellin were attributed to industrial emissions. Ni in Lima was associated with emissions from metal smelting facilities and ship heavy oil combustion. Higher total PAH concentrations and benzo[a]pyrene equivalent (BaPE) index in Sao Paulo indicated a stronger influence of vehicular exhaust in this megacity. The results highlighted the importance of biomass burning and vehicular sources for Sao Paulo, vehicular exhaust, biomass burning, and industrial sources for Medellin, and marine aerosol, together with vehicular, industrial, and ship exhaust, for Lima.

The main sources of particulate emissions from engines are fuel and lubricating oil. In this study, particles emitted by a medium speed diesel engine for locomotive use were characterized chemicall...

High spatial resolution particulate matter measurements are necessary to accurately characterize urban air quality issues. This study investigates how sensors can be used in an urban area to complement existing air quality measurements. A measurement campaign was conducted during winter in Helsinki, Finland, where the performance of a custom-built optical instrument—the Prototype Aerosol Sensor (PAS; uses Shinyei PPD60PV and PPD42NS sensor modules)—and three commercial diffusion charging-based sensors (Pegasor AQ Urban, DiSCmini and Partector) was evaluated against reference instruments. The results showed that the PAS was able to measure the coarse (PM2.5-10; range: 0–400 µg m–3) and fine (PM2.5; range: 0–50 µg m–3) fractions with reasonably high correlations (R2 = 0.87 and 0.77) when compared to a gravimetric monitor. Likewise, the lung deposited surface area (LDSA) concentrations delivered by the three diffusion charging sensors indicated good performance (R2: 0.92–0.97) when compared to LDSA concentrations calculated from the size distribution data of the differential mobility particle sizer. A clear correlation (R2 = 0.77) between the black carbon and Pegasor-measured LDSA concentrations, as well as similar diurnal cycles, was observed, suggesting a common source. The optical sensors were useful for measuring the mass concentrations of coarse local particles. By contrast, the diffusion charging sensors were applicable in urban environments, where ultrafine particles from traffic or other local combustion sources affect air quality.

Coal combustion is one of the most significant anthropogenic CO2 and air pollution sources globally. This paper studies the atmospheric emissions of a power plant fuelled with a mixture of industrial pellets (10.5%) and coal (89.5%). Based on the stack measurements, the solid particle number emission, which was dominated by sub-200 nm particles, was 3.4×1011 MJ-1 for the fuel mixture when electrostatic precipitator (ESP) was cleaning the flue gas. The emission factor was 50 mg MJ-1 for particulate mass and 11 740 ng MJ-1 for the black carbon with the ESP. In the normal operation situation of the power plant, i.e., including the flue-gas desulphurisation and fabric filters (FGD and FF), the particle number emission factor was 1.7×108 MJ-1, particulate mass emission factor 2 mg MJ-1 and black carbon emission factor 14 ng MJ-1. Transmission electron microscopy (TEM) analysis supported the particle number size distribution measurement in terms of particle size and the black carbon concentration. The TEM images of the particles showed variability of the particle sizes, morphologies and chemical compositions. The atmospheric measurements, conducted in the flue-gas plume, showed that the flue-gas dilutes closed to background concentrations in 200 sec. However, an increase in particle number concentration was observed when the flue gas aged. This increase in particle number concentration was interpret as formation of new particles in the atmosphere. In general, the study highlights the importance of detailed particle measurements when utilizing new fuels in existing power plants. Implications: CO2 emissions of energy production decrease when substituting coal with biofuels. The effects of fuels changes on particle emission characteristics have not been studied comprehensively. In this study conducted for a real-scale power plant, co-combustion of wood pellets and coal caused elevated black carbon emissions. However, it was beneficial from the total particle number and particulate mass emission point of view. Flue-gas cleaning can significantly decrease the pollutant concentrations but also changes the characteristics of emitted particles. Atmospheric measurements implicated that the new particle formation in the atmospheric flue-gas plume should be taken into account when evaluating all effects of fuel changes.” Are implication statements part of the manuscript?

Shipping is the main source of anthropogenic particle emissions in large areas of the globe, influencing climate, air quality, and human health in open seas and coast lines. Here, we determined, by laboratory and on-board measurements of ship engine exhaust, fuel-specific particle number (PN) emissions for different fuels and desulfurization applied in shipping. The emission factors were compared to ship exhaust plume observations and, furthermore, exploited in the assessment of global PN emissions from shipping, utilizing the STEAM ship emission model. The results indicate that most particles in the fresh ship engine exhaust are in ultrafine particle size range. Shipping PN emissions are localized, especially close to coastal lines, but significant emissions also exist on open seas and oceans. The global annual PN produced by marine shipping was 1.2 × 1028 (±0.34 × 1028) particles in 2016, thus being of the same magnitude with total anthropogenic PN emissions in continental areas. The reduction potential of PN from shipping strongly depends on the adopted technology mix, and except wide adoption of natural gas or scrubbers, no significant decrease in global PN is expected if heavy fuel oil is mainly replaced by low sulfur residual fuels. The results imply that shipping remains as a significant source of anthropogenic PN emissions that should be considered in future climate and health impact models. acceptedVersion

Natural gas usage in traffic and energy production sector is a growing trend worldwide, thus an assessment of its effects on air quality, human health and climate is required. Engine exhaust is a source of primary particulate emissions and secondary aerosol precursors that both contribute to air quality and can cause adverse health effects. Technologies, such as cleaner engines or fuels, that produce less primary and secondary aerosol could potentially significantly decrease the atmospheric particle concentrations and their adverse effects. In this study, we used a potential aerosol mass (PAM) chamber to investigate the secondary aerosol formation potential of natural gas engine exhaust. The PAM chamber was used with a constant UV-light voltage that resulted in an equivalent atmospheric age of 11 days at a maximum. The studied passenger car engine, retrofitted to run with natural gas, was observed to have a low or moderate secondary particle formation potential, although the simulated atmospheric ages were relatively long. The secondary organic aerosol (SOA) formation potential was measured to be 8–18 mg kgfuel−1. However, the mass of total aged particles, i.e. particle mass measured downstream the PAM chamber, was 6–184 times as high as the mass of the emitted primary exhaust particles. The total aged particles consisted mainly of nitrate, organic matter, sulfate and ammonium, the fractions depending on exhaust after-treatment and used engine parameters. Also the volatility, composition and concentration of the total aged particles were found to depend on the engine operating mode, catalyst temperature and catalyst type. For example, a high catalyst temperature promoted the formation of sulfate particles, whereas a low catalyst temperature promoted nitrate formation. However, especially the concentration of nitrate needed a long time, more than half an hour, to stabilize, which complicated the conclusions but also indicates the sensitivity of nitrate measurements on experimental parameters such as emission source and system temperatures. Sulfate was measured to have the highest evaporation temperature and nitrate the lowest. The evaporation temperature of ammonium depended on the fractions of nitrate and sulfate in the particles. The average volatility of the total aged particles was measured to be lower than that of primary particles, indicating better stability of the aged natural gas engine emitted aerosol in the atmosphere. According to the results of this study, the shift from traditional liquid fuels to natural gas can have a decreasing effect on total particle pollution in the atmosphere; in addition to the very low primary particle emissions, also the secondary organic aerosol formation potential of natural gas exhaust is lower or on the same level as the SOA formation potential measured on liquid fuels in previous studies.

A two-week measurement campaign by a mobile laboratory van was performed in urban environments in the Helsinki metropolitan area, Finland, in winter 2012, to obtain a comprehensive view on aerosol properties and sources. The abundances and physico-chemical properties of particles varied strongly in time and space, depending on the main sources of aerosols. Four major types of winter aerosol were recognized: 1) clean background aerosol with low particle number (Ntot) and lung deposited surface area (LDSA) concentrations due to marine air flows from the Atlantic Ocean; 2) long-range transported (LRT) pollution aerosol due to air flows from eastern Europe where the particles were characterized by the high contribution of oxygenated organic aerosol (OOA) and inorganic species, particularly sulphate, but low BC contribution, and their size distribution possessed an additional accumulation mode; 3) fresh smoke plumes from residential wood combustion in suburban small houses, these particles were characterized by high biomass burning organic aerosol (BBOA) and black carbon (BC) concentrations; and 4) fresh emissions from traffic while driving on busy streets in the city centre and on the highways during morning rush hours. This aerosol was characterized by high concentration of Ntot, LDSA, small particles in the nucleation mode, as well as high hydrocarbon-like organic aerosol (HOA) and BC concentrations. In general, secondary components (OOA, NO3, NH4, and SO4) dominated the PM1 chemical composition during the LRT episode accounting for 70–80% of the PM1 mass, whereas fresh primary emissions (BC, HOA and BBOA) dominated the local traffic and wood burning emissions. The major individual particle types observed with electron microscopy analysis (TEM/EDX) were mainly related to residential wood combustion (K/S/C-rich, soot, other C-rich particles), traffic (soot, Si/Al-rich, Fe-rich), heavy fuel oil combustion in heat plants or ships (S with V-Ni-Fe), LRT pollutants (S/C-rich secondary particles) and sea salt (Na/Cl-rich). Tar balls from wood combustion were also observed, especially (∼5%) during the LRT pollution episode. acceptedVersion

The effect of fuel ethanol content (10, 85 and 100 %) on primary emissions and on subsequent secondary aerosol formation was investigated for a Euro 5 flex-fuel gasoline vehicle. Emissions were characterized during a New European Driving Cycle (NEDC) using a comprehensive set-up of high time-resolution instruments. A detailed chemical composition of the exhaust particulate matter (PM) was studied using a soot particle aerosol mass spectrometer (SP-AMS), and secondary aerosol formation was studied using a potential aerosol mass (PAM) chamber. For the primary gaseous compounds, an increase in total hydrocarbon emissions and a decrease in aromatic BTEX (benzene, toluene, ethylbenzene and xylenes) compounds was observed when the amount of ethanol in the fuel increased. In regard to particles, the largest primary particulate matter concentrations and potential for secondary particle formation was measured for the E10 fuel (10 % ethanol). As the ethanol content of the fuel increased, a significant decrease in the average primary particulate matter concentrations over the NEDC was found. The PM emissions were 0.45, 0.25 and 0.15 mg m−3 for E10, E85 and E100, respectively. Similarly, a clear decrease in secondary aerosol formation potential was observed with a larger contribution of ethanol in the fuel. The secondary-to-primary PM ratios were 13.4 and 1.5 for E10 and E85, respectively. For E100, a slight decrease in PM mass was observed after the PAM chamber, indicating that the PM produced by secondary aerosol formation was less than the PM lost through wall losses or the degradation of the primary organic aerosol (POA) in the chamber. For all fuel blends, the formed secondary aerosol consisted mostly of organic compounds. For E10, the contribution of organic compounds containing oxygen increased from 35 %, measured for primary organics, to 62 % after the PAM chamber. For E85, the contribution of organic compounds containing oxygen increased from 42 % (primary) to 57 % (after the PAM chamber), whereas for E100 the amount of oxidized organics remained the same (approximately 62 %) with the PAM chamber when compared to the primary emissions.

Fossil fuel combustion should be decreased in future years in order to lower the CO2 emissions of energy production. The reduction can be achieved by increasing the amount of CO2-neutral fuels in energy production. Here 6-13% of coal was substituted with industrial or roasted pellets in a pulverized fuel-fired power plant without making any changes to fuel grinding or low-NOx burners. The effect of pellet addition for the flue gas particles was studied with direct sampling from the boiler super heater area. Based on primary dilution ratio tests, transmission electron microscope images, and the natural electric charge of the particles, it was observed that particles in the flue gas are spherical and have been formed in the boiler at high temperatures. The pellet addition lowered the total particle number concentrations with all of the studied pellet-coal mixtures in comparison to the coal combustion. The 10.5% industrial pellet addition caused a second mode in the particle number size distribution. In addition, based on the chemical analysis of the collected size-fractioned particle samples, results indicated that the pellet addition did not increase the corrosion risk of the boiler. However, the changes in the particle number size distribution and total particle number concentration can affect the operation of electrostatic precipitators and flue gas cleaning.

Particulate matter (PM) from mining operations, engines, and ore processing may have adverse effects on health and well-being of workers and population living nearby. In this study, the characteristics of PM in an underground chrome mine were investigated in Kemi, Northern Finland. The concentrations and chemical composition of PM in size ranges from 2.5 nm to 10 µm were explored in order to identify sources, formation mechanisms, and post-emission processes of particles in the mine air. This was done by using several online instruments with high time-resolution and offline particulate sampling followed by elemental and ionic analyses. A majority of sub-micrometer particles (1) originated from diesel engine emissions that were responsible for a rather stable composition of PM1 in the mine air. Another sub-micrometer particle type originated from the combustion products of explosives (e.g., nitrate and ammonium). On average, PM1 in the mine was composed of 62%, 30%, and 8% of organic matter, black carbon, and major inorganic species, respectively. Regarding the analyzed elements (e.g., Al, Si, Fe, Ca), many of them peaked at >1 µm indicating mineral dust origin. The average particle number concentration in the mine was (2.3 ± 1.4)*104 #/cm3. The maximum of particle number size distribution was between 30 and 200 nm for most of the time but there was frequently a distinct mode

Chemical characteristics and the sources of submicron particles (

Lung deposited surface area (LDSA) concentration is considered as a relevant metric for the negative health effects of aerosol particles. We report for the first time the size distributions of the LDSA measured in urban air. The measurements were carried out in the metropolitan area of Helsinki, including mobile laboratory and stationary measurements in different outdoor environments, such as traffic sites, a park area, the city center and residential areas. The main instrument in this study was an electrical low pressure impactor (ELPI), which was calibrated in the field to measure the LDSA concentration. The calibration factor was determined to be 60 μm2/(cm3 pA). In the experiments, the LDSA size distributions were found to form two modes at the traffic sites and in the city center. Both of these traffic related particle modes, the nucleation mode and the soot mode, had a clear contribution to the total LDSA concentration. The average total concentrations varied from 12 to 94 μm2/cm3, measured in the park area and at the traffic site next to a major road, respectively. The LDSA concentration was found to correlate with the mass of fine particles (PM2.5), but the relation of these two metrics varied between different environments, emphasizing the influence of traffic on the LDSA. The results of this study provide valuable information on the total concentrations and size distributions of the LDSA for epidemiological studies. The size distributions are especially important in estimating the contribution of outdoor concentrations on the concentrations inside buildings and vehicles through size-dependent penetration factors. publishedVersion

Exhaust emissions of 23 individual city buses at Euro III, Euro IV and EEV (Enhanced Environmentally Friendly Vehicle) emission levels were measured by the chasing method under real-world conditions at a depot area and on the normal route of bus line 24 in Helsinki. The buses represented different technologies from the viewpoint of engines, exhaust after-treatment systems (ATS) and fuels. Some of the EEV buses were fueled by diesel, diesel-electric, ethanol (RED95) and compressed natural gas (CNG). At the depot area the emission factors were in the range of 0.3-21 × 10(14) # (kg fuel)(-1), 6-40 g (kg fuel)(-1), 0.004-0.88 g (kg fuel)(-1), 0.004-0.56 g (kg fuel)(-1), 0.01-1.2 g (kg fuel)(-1), for particle number (EFN), nitrogen oxides (EFNOx), black carbon (EFBC), organics (EFOrg), and particle mass (EFPM1), respectively. The highest particulate emissions were observed from the Euro III and Euro IV buses and the lowest from the ethanol and CNG-fueled buses, which emitted BC only during acceleration. The organics emitted from the CNG-fueled buses were clearly less oxidized compared to the other bus types. The bus line experiments showed that lowest emissions were obtained from the ethanol-fueled buses whereas large variation existed between individual buses of the same type indicating that the operating conditions by drivers had large effect on the emissions.

Urban air contains considerable amounts of harmful gaseous substances and aerosol particles. In this study, a recently introduced diffusion charger based PPS-M particle sensor (Pegasor Oy, Tampere, Finland) was evaluated for outdoor air quality measurements in urban environment. The PPS-M particle sensor was used in two stationary air quality measurement stations, one located in the roadside environment and the other in residential area, and in a mobile laboratory. The sampling of urban aerosol to the PPS-M sensor was performed without any pre-conditioning of aerosol. The sensor response to PM 2.5 varied between the measurements, being between 7 and 30 fA/(μg/m 3 ) depending on the aerosol source. The highest PM 2.5 response was observed in the roadside study for exhaust particles while the lowest PM 2.5 response was observed for large long range transported aerosol particles having relatively large mean particle size. The sensor signal was found to produce very linear response, with only minimal deviation, to the lung deposited particle surface area concentration (from 4.5 to 6 fA/(μm 2 /cm 3 )) and to the condensation sink of urban air particles (from 1.0 × 10 4 to 1.2 × 10 4 fA cm 3 ). The sensor response to particle number concentration was defined to be 0.0044 fA/(1/cm 3 ) in roadside environment. In this environment, the signal was found to correlate also with NO and NO 2 concentrations of roadside air due to the same origin of particulate and gaseous pollutants. Similar correlation between NO x and the PPS-M signal was not observed in residential area.

A method to detect and quantify mass concentrations of trace metals on soot particles by the Aerodyne soot-particle aerosol mass spectrometer (SP-AMS) was developed and evaluated in this study. The generation of monodisperse Regal black (RB) test particles with trace amounts of 13 different metals (Na, Al, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr and Ba) allowed for the determination of the relative ionization efficiency of each metal relative to black carbon (RIEmeas). The observed RIEmeas / RIEtheory values were larger than unity for Na, Rb, Ca, Sr and Ba due to thermal surface ionization (TSI) on the surface of the laser-heated RB particles. Values closer to unity were obtained for the transition metals Zn, Cu, V and Cr. Mn, Fe, and Ni presented the lowest RIEmeas / RIEtheory ratios and highest deviation from unity. The latter discrepancy is unexplained; however it may be related to problems with our calibration method and/or the formation of metal complexes that were not successfully quantified. The response of the metals to the laser power was investigated and the results indicated that a minimum pump laser current of 0.6 A was needed in order to vaporize the metals and the refractory black carbon (rBC). Isotopic patterns of metals were resolved from high-resolution mass spectra, and the mass-weighted size distributions for each individual metal ion were obtained using the high-resolution particle time-of-flight (HR-PToF) method. The RIEmeas values obtained in this study were applied to the data of emission measurements in a heavy-fuel-oil-fired heating station. Emission measurements revealed a large number of trace metals, including evidence for metal oxides and metallic salts, such as vanadium sulfate, calcium sulfate, iron sulfate and barium sulfate, which were identified in the SP-AMS high-resolution mass spectra. SP-AMS measurements of Ba, Fe, and V agreed with ICP-MS analyzed filter samples within a factor of 2 when emitted rBC mass loadings were elevated.

Inexpensive aerosol sensors have been considered as a complementary option to address the issue of expensive but low spatial coverage air quality monitoring networks. However, the accuracy and response characteristics of these sensors is poorly documented. In this study, inexpensive Shinyei PPD42NS and PPD60PV sensors were evaluated using a novel laboratory evaluation method. A continuously changing monodisperse size distribution of particles was generated using a Vibrating Orifice Aerosol Generator. Furthermore, the laboratory results were validated in a field experiment. The laboratory tests showed that both of the sensors responded to particulate mass (PM) concentration stimulus, rather than number concentration. The highest detection efficiency for the PPD42NS was within particle size range of 2.5–4 µm, and the respective optimal size range for the PPD60PV was 0.7–1 µm. The field test yielded high PM correlations (R2 = 0.962 and R2 = 0.986) for viable detection ranges of 1.6–5 and 0.3–1.6 µm, when compared to a medium cost optical dust monitor. As the size distribution of atmospheric particles tends to be bimodal, it is likely that indicatively valid results could be obtained for the PM10–2.5 size fraction (particulate mass in size range 2.5–10 µm) with the PPD42NS sensor. Respectively, the PPD60PV could possibly be used to measure the PM2.5 size fraction (particulate mass in size below 2.5 µm).

Logs of three common Southern and mid-European woods (Quercus pyrenaica, Populus nigra and Fagus sylvatica) were burned in two different combustion appliances, a fireplace and a stove. The flue gas composition was monitored continuously in the exhaust ducts of both burning appliances for total hydrocarbons (THC) and carbon oxides (CO2 and CO). Particulate matter with aerodynamic diameter below 2.5 μm (PM2.5) was sampled in a dilution tunnel under isokinetic conditions and chemically characterised for water soluble-inorganic ions, organic and elemental carbon and levoglucosan, mannosan, and galactosan. The evolution of the emission factors of these components throughout the combustion cycle was studied. The fireplace was the combustion appliance with the highest CO, CO2, THC and PM2.5 emission factors. The carbonaceous matter represented 72–84% of the particulate mass emitted, regardless of species burned and combustion devices. OC/EC ratios were higher for the fireplace than for the stove, and showed a significant potential relation with K+/levoglucosan. The dominant water soluble inorganic ions in smoke particles were K+, PO 4 3 − , SO 4 2 − , and Na+. Anhydrosugar emissions were strongly enhanced in the start-up phase, when lower temperatures are registered, and decreased progressively until the glowing combustion phase. However, K+ emission seems to be higher in flaming-dominated combustion at higher temperature. Statistical analyses, including the Kruskal–Wallis test, principal component analysis and Pearson correlation between emission factors, were carried out. A significant correlation between NH4+ and levoglucosan was found for both appliances.

The chemical and microbial composition of urban air particulate matter (PM) displays seasonal variation that may affect its harmfulness on human health. We studied the in vitro inflammatory and cellular metabolic activity/cytotoxicity of urban air particulate samples collected in four size-ranges (PM10-2.5, PM2.5-1, PM1-0.2, PM0.2) during four seasons in relatively clean urban environment in Helsinki, Finland. The composition of the same samples were analyzed, including ions, elements, PAH compounds and endotoxins. In addition, microbial contribution on the detected responses was studied by inhibiting the endotoxin-induced responses with Polymyxin B both in the PM samples and by two different bacterial strains representing Gram-positive and -negative bacteria. Macrophage cell line (RAW 264.7) was exposed to the size segregated particulate samples as well as to microbe samples for 24h and markers of inflammation and cytotoxicity were analyzed. The toxicological responses were dependent on the dose as well as size range of the particles, PM10-2.5 being the most potent and smaller size ranges having significantly smaller responses. Samples collected during spring and autumn had in most cases the highest inflammatory activity. Soil components and other non-exhaust particulate emissions from road traffic correlated with inflammatory responses in coarse particles. Instead, PAH-compounds and K(+) had negative associations with the particle-induced inflammatory responses in fine particles, suggesting the role of incomplete biomass combustion. Endotoxin content was the highest in PM10-2.5 samples and correspondingly, the largest decrease in the responses by Polymyxin B was seen with the very same samples. We found also that inhibitory effect of Polymyxin B was not completely specific for Gram-negative bacteria. Thus, in addition to endotoxin, also other microbial components may have a significant effect on the toxicological responses by ambient particulate matter.

Natural gas engine particle emissions were studied using an old gasoline engine modified to run with natural gas. The tests were steady-state tests performed on two different low loads in an engine dynamometer. Exhaust particle number concentration, size distribution, volatility and electric charge were measured. Exhaust particles were observed to have peak diameters below 10 nm. To get the full picture of particle emissions from natural gas engines, size range 1–5 nm is relevant and important to take into consideration. A particle size magnifier (PSM) was used in this engine application for measuring particles smaller than 3 nm and it proved to be a useful instrument when measuring natural gas engine exhaust particles. It is concluded that the detected particles probably originated from the engine cylinders or their vicinity and grew to detectable sizes in the sampling process because a small fraction of the particles were observed to carry electric charge and the particles did not evaporate totally at 265 °C.

A recently introduced fluorescence based real-time bioaerosol instrument, BioScout, and an ultraviolet aerodynamic particle sizer (UVAPS) were used to study fluorescent bioaerosol particles (FBAP) in the Helsinki metropolitan area, Finland, during winter and summer. Two FBAP modes at 0.5–1.5 µm (fine) and 1.5–5 µm (coarse) were detected during the summer, whereas the fine mode dominated in the winter. The concentration and proportion of the coarse FBAP was high in summer (0.028 #/cm 3 , 23%) and low in winter (0.010 #/cm 3 , 6%). Snow cover and low biological activity were assumed to be the main reasons for the low coarse FBAP concentration in the wintertime. Both the fine and the coarse FBAP fraction typically increased at nighttime during the summer. Correlations between the BioScout and the UVAPS were high with the coarse (R = 0.83) and fine (R = 0.92) FBAP. The BioScout showed 2.6 and 9.7 times higher detection efficiencies for the coarse and fine FBAP, respectively, compared to the UVAPS. A long-range transport episode of particles from Eastern Europe increased the fine FBAP concentration by over two orders of magnitude compared to the clean period in the winter, but these FBAP probably also included fluorescent non-biological particles. Correlation analysis indicates that local combustion sources did not generate fluorescent non-biological particles that can disturb fine FBAP counting. The results provide information that can be used to estimate health risks and climatic relevance of bioaerosols in the urban environment.

Chemical characterization of non-refractory submicron particles (NR-PM1) and source apportionment of organic aerosols (OA) were carried out at four different sites in the Helsinki metropolitan area, Finland, using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Two of the sites represented suburban residential areas, whereas the other two were traffic sites, one in a curbside in downtown and the other one in a suburban highway edge. The residential and the curbside measurements were conducted during the winter, but the highway campaign was carried out in the autumn. NR-PM1 were composed mainly of organics (40–68% in the different sites), followed by sulphate (11–34%), nitrate (12–16%), ammonium (7.8–8.5%) and chloride (0.24–1.3%). The mean concentrations of NR-PM1 were quite similar during the winter campaigns (10.1–12.5 µg/m3), but NR-PM1 was clearly lower during the autumn campaign at the highway site (6.0 µg/m3) due to the meteorology (favourable mixing conditions), small concentrations of long-range transported particles and non-intensive heating period locally and regionally. Using a multilinear engine algorithm (ME-2) and the custom software tool Source Finder (SoFI), the organic fraction was divided into two or three types of OA representing hydrocarbon-like organic aerosol (HOA), oxygenated organic aerosol (OOA), and in three sites, biomass burning organic aerosol (BBOA). At the downtown traffic site (Curbside), BBOA could not be found, probably because most of the local wood burning occurs in the suburban areas of the Helsinki region. OOA had the largest contribution to OA at all the sites (50–67%). The contribution of HOA was higher at the traffic sites (25–32%) than at the residential sites (15–18%). At the suburban residential and highway sites, the contribution of BBOA was high (25–30%). Especially during cold periods, very high BBOA contributions (~50%) were observed at the residential sites.

In densely populated areas, traffic is a significant source of atmospheric aerosol particles. Owing to their small size and complicated chemical and physical characteristics, atmospheric particles resulting from traffic emissions pose a significant risk to human health and also contribute to anthropogenic forcing of climate. Previous research has established that vehicles directly emit primary aerosol particles and also contribute to secondary aerosol particle formation by emitting aerosol precursors. Here, we extend the urban atmospheric aerosol characterization to cover nanocluster aerosol (NCA) particles and show that a major fraction of particles emitted by road transportation are in a previously unmeasured size range of 1.3–3.0 nm. For instance, in a semiurban roadside environment, the NCA represented 20–54% of the total particle concentration in ambient air. The observed NCA concentrations varied significantly depending on the traffic rate and wind direction. The emission factors of NCA for traffic were 2.4·1015 (kgfuel)−1 in a roadside environment, 2.6·1015 (kgfuel)−1 in a street canyon, and 2.9·1015 (kgfuel)−1 in an on-road study throughout Europe. Interestingly, these emissions were not associated with all vehicles. In engine laboratory experiments, the emission factor of exhaust NCA varied from a relatively low value of 1.6·1012 (kgfuel)−1 to a high value of 4.3·1015 (kgfuel)−1. These NCA emissions directly affect particle concentrations and human exposure to nanosized aerosol in urban areas, and potentially may act as nanosized condensation nuclei for the condensation of atmospheric low-volatile organic compounds. acceptedVersion acceptedVersion

São Paulo in Brazil has relatively relaxed regulations for ambient air pollution standards and often experiences high air pollution levels due to emissions of airborne particles from local sources and long-range transport of biomass burning-impacted air masses. In order to evaluate the sources of particulate air pollution (PM) and related health risks, a year-round sampling was performed for PM2.5 (≤ 2.5 μm) and PM10 (≤ 10 μm) in 2014 through intensive (every day sampling in wintertime) and extensive campaigns (once a week for the whole year) with 24 h of sampling. This year was characterized to have lower average precipitation comparing to meteorological data, and high pollution episodes were observed all year round, with a significant increase of pollution level in the intensive campaign, which was performed during wintertime. Different chemical constituents, such as carbonaceous species, polycyclic aromatic hydrocarbons (PAHs) and derivatives, water-soluble ions and biomass burning tracers were identified in order to evaluate health risks and to apportion sources. The species such as PAHs, inorganic and organic ions and monosaccharides were determined by chromatographic techniques and carbonaceous species by thermal-optical analysis. The associated risks to particulate matter exposure based on PAH concentrations were also assessed, along with indexes such as the benzo[a]pyrene equivalent (BaPE) and lung cancer risk (LCR). High BaPE and LCR were observed in most of the samples, rising to critical values in the wintertime. Also, biomass burning tracers and PAHs were higher in this season, while secondarily formed ions presented low variation throughout the year. Meanwhile, vehicular tracer species were also higher in the intensive campaign suggesting the influence of lower dispersion conditions in that period. Source apportionment was done by Positive Matrix Factorization (PMF), which indicated five different factors: road dust, industrial emissions, vehicular exhaust, biomass burning and secondary processes. The results highlighted the contribution of vehicular emissions and the significant input from biomass combustion in wintertime, suggesting that most of the particulate matter is due to local sources, besides the influence of pre-harvest sugarcane burning.

In this article we present a design of a new miniaturized sensor with the capacity to measure exhaust particle concentrations on board vehicles and engines. The sensor is characterized by ultra-fast response time, high sensitivity, and a wide dynamic range. In addition, the physical dimensions of the sensor enable its placement along the exhaust line. The concentration response and temporal performance of a prototype sensor are discussed and characterized with aerosol laboratory test measurements. The sensor performance was also tested with actual engine exhaust in both chassis and engine dynamometer measurements. These measurements demonstrate that the sensor has the potential to meet and even exceed any requirements around the world in terms of on-board diagnostic (OBD) sensitivity and frequency of monitoring. Further to potential OBD applications, this has the capacity to be used as an engine and combustion diagnostics sensor, for example to detect misfiring, cylinder combustion variability, exhaust gas recirculation flowrate, etc. acceptedVersion

Sao Paulo is a Latin American megacity impacted by heavy traffic emissions and also affected by biomass burning and biogenic emissions. To better understand the sources of pollution during a highly polluted period, PM10 samples were collected in an intensive campaign in 2013. The concentrations of particulate matter, organic carbon (OC), elemental carbon (EC), biomass burning tracers (levoglucosan, mannosan, and galactosan), water-soluble ions, and polycyclic aromatic hydrocarbons (PAHs) were determined to identify the main sources affecting the air quality. The PAHs results were compared to an intensive campaign done in 2012. Backward air masses trajectories were used in other to investigate the influence of remote sources. The average benzo[a]pyrene equivalent index (BaPE) values represented a higher cancer risk in 2013 samples than in 2012; the diagnostic ratios indicated vehicular emissions for both campaigns but fresher particles emission for 2013 campaign. During the 2013 campaign, the samples presented good correlations between OC and EC with monosaccharides, suggesting an influence of biomass burning on the carbonaceous species. Levoglucosan to mannosan ratio indicated the influence of sugarcane burning; the backward air masses trajectories suggested transport of aerosol from the sugarcane production region in 60 % of the sampling days.

Detailed chemical characterization of exhaust particles from 23 individual city buses was performed in Helsinki, Finland. Investigated buses represented different technologies in terms of engines, exhaust after-treatment systems (e.g., diesel particulate filter, selective catalytic reduction, and three-way catalyst) and fuels (diesel, diesel-electric (hybrid), ethanol, and compressed natural gas). Regarding emission standards, the buses operated at EURO III, EURO IV, and EEV (enhanced environmentally friendly vehicle) emission levels. The chemical composition of exhaust particles was determined by using a soot particle aerosol mass spectrometer (SP-AMS). Based on the SP-AMS results, the bus emission particles were dominated by organics and refractory black carbon (rBC). The mass spectra of organics consisted mostly of hydrocarbon fragments (54-86% of total organics), the pattern of hydrocarbon fragments being rather similar regardless of the bus type. Regarding oxygenated organic fragments, ethanol-fueled buses had unique mass-to-charge ratios (m/z) of 45, 73, 87, and 89 (mass fragments of C2H5OC, C3H5O2+, C4H7O2+, and C4H9O2+, respectively) that were not detected for the other bus types at the same level. For rBC, there was a small difference in the ratio of C-4(+) and C-5(+) to C-3(+) for different bus types but also for the individual buses of the same type. In addition to organics and rBC, the presence of trace metals in the bus emission particles was investigated.

The performance of the miniature Versatile Aerosol Concentration Enrichment System (m-VACES; Geller et al., 2005) was investigated in laboratory and field studies using online instruments. Laboratory tests focused on the behavior of monodisperse ammonium sulfate (AS) or dioctyl sebacate (DOS) particles in the m-VACES measured with the aerodynamic particle sizer (APS) and scanning mobility particle sizer (SMPS). The ambient measurements were conducted at an urban site in Helsinki, Finland, where the operation of the m-VACES was explored in conjunction with a Soot Particle Aerosol Mass Spectrometer (SP-AMS) in addition to the SMPS. In laboratory tests, the growth of particles in water vapor produced a stable droplet size distribution independent of the original particle size. However, when the droplets were dried with the goal of measuring the original size distribution, a shift to larger particles was observed for small particle sizes (up to ~ 200 nm in mobility diameter). That growth was probably caused by water-soluble organic compounds absorbed on the water droplets from the gas phase, but not evaporated in the drying phase. In ambient measurements, a similar enrichment was observed for nitrate and sulfate in the m-VACES whereas the presence of acidic ambient particles affected the enrichment of ammonium. Gaseous ammonia was likely to be absorbed on acidic particles in the m-VACES, neutralizing the aerosol. For organics, the enrichment efficiency was comparable with sulfate and nitrate but a small positive artifact for hydrocarbons and nitrogen-containing organic compounds was noticed. Ambient and concentrated organic aerosol (OA) was analyzed further with positive matrix factorization (PMF). A three-factor solution was chosen for both of the data sets but the factors were slightly different for the ambient and concentrated OA, however, the data set used for the PMF analysis was limited in size (3 days) and therefore had substantial uncertainty. Overall, the operation of the m-VACES was not found to lead to any severe sampling artifacts. The effect of acidity could be an issue in locations where the aerosol is acidic, however, in those cases the use of a denuder (which was not used in this study) is recommended. Further ambient tests are needed for the characterization of the m-VACES as the time period for the ambient measurements was only 5 days in this study. Especially for OA additional tests are important as the chemical properties of organics can differ widely depending on time and location.

Globally more than a quarter of the total primary energy supply is based on coal combustion. The emissions of coal-fired power plants (CFPPs) are regulated in many industrialized countries and therefore power plants use cleaning techniques to minimize emissions such as sulfur dioxide (SO 2 ) and particles. In this study, the particulate emissions from coal combustion were investigated at a CFPP (506 MW) used for combined heat and power production in Helsinki, Finland. Fine particle samples (PM 1 ) were collected after electrostatic precipitator before the desulfurization plant (DSP), including flue gas desulfurization unit (FGD) and baghouse filters, and simultaneously in the smokestack to study the influence of DSP to particulate mass and chemistry. The DSP removed over 97% of particle mass in flue gas. Trace metals were removed efficiently but contribution of some ionic compounds increased in the FGD process. The particle properties were studied in more detail in the smokestack including particle size distribution measurements and size-segregating sampling to study chemical composition and morphology of particles. The particulate emissions from the CFPP were relatively small, consisting mainly of products and reagents of the FGD process (e.g., CaSO 4 , NaCl) and partly of the primary emissions from the coal combustion (e.g., mineral ash and reaction products of gas phase components). The maximum in particle volume was detected at 0.68 µm. PM 1 contributed on average 62 ± 5% to PM 10 mass. Besides particulate matter, also the gas-phase emission of mercury was studied because coal combustion is one of the major sources of mercury found in the environment. The mercury emissions were within the proposed limits in the EU.

The current study presents, for the first time, a long-term organic speciation of aerosol at the Cape Verde archipelago. The Cape Verde location, in the Atlantic Ocean, provides a unique laboratory to study background aerosol, long-range transport, aerosol mixing with mineral dust, biomass burning and sea surface components. In order to contribute to a better understanding of this environment, a one-year long measurement campaign was performed in Praia City, Santiago Island. PM 10 concentrations (20.5–370 μg/m 3 ) and the organic composition of PM 10 were influenced by the African dust influxes. The carbonaceous content of PM 10 was very low, suggesting that most of the mass has mineral origin. The PM 10 composition was essentially characterised by a large variety of organic compounds, which can be grouped into general compound classes, such as n -alkanes, n -alkanols, n -acids and sugars. The n -alkane total concentrations varied from 3.77 to 53.2 ng/m 3 . The n -alkanols distribution showed a significant biogenic contribution whether from microbial origin or from epicuticular plants during African dust outbreaks. The total concentrations of n -alkanoic acids varied from 0.011 to 4.51 ng/m 3 . The lower n -alkenoic acids content, obtained during the periods of long-range transport from Africa, indicated a more aged aerosol. The monosaccharide anhydrides were detected in all samples with a range of concentrations from 2.06 to 12.7 ng/m 3 .

Atmospheric organic aerosols are generally classified as primary and secondary (POA and SOA) according to their formation processes. An actual separation, however, is challenging when the timescales of emission and gas-to-particle formation overlap. The presence of SOA formation in biomass burning plumes leads to scientific questions about whether the oxidized fraction of biomass burning aerosol is rather of secondary or primary origin, as some studies would suggest, and about the chemical compositions of oxidized biomass burning POA and SOA. In this study, we apply nuclear magnetic resonance (NMR) spectroscopy to investigate the functional group composition of fresh and aged biomass burning aerosols during an intensive field campaign in the Po Valley, Italy. The campaign was part of the EUCAARI project and was held at the rural station of San Pietro Capofiume in spring 2008. Factor analysis applied to the set of NMR spectra was used to apportion the wood burning contribution and other organic carbon (OC) source contributions, including aliphatic amines. Our NMR results, referred to the polar, water-soluble fraction of OC, show that fresh wood burning particles are composed of polyols and aromatic compounds, with a sharp resemblance to wood burning POA produced in wood stoves, while aged samples are clearly depleted of alcohols and are enriched in aliphatic acids with a smaller contribution of aromatic compounds. The comparison with biomass burning organic aerosols (BBOA) determined by high-resolution aerosol mass spectrometry (HR-TOF-AMS) at the site shows only a partial overlap between NMR BB-POA and AMS BBOA, which can be explained by either the inability of BBOA to capture all BB-POA composition, especially the alcohol fraction, or the fact that BBOA account for insoluble organic compounds unmeasured by the NMR. Therefore, an unambiguous composition for biomass burning POA could not be derived from this study, with NMR analysis indicating a higher O / C ratio compared to that measured for AMS BBOA. The comparison between the two techniques substantially improves when adding factors tracing possible contributions from biomass burning SOA, showing that the operational definitions of biomass burning organic aerosols are more consistent between techniques when including more factors tracing chemical classes over a range of oxidation levels. Overall, the non-fossil total carbon fraction was 50–57%, depending on the assumptions about the 14C content of non-fossil carbon, and the fraction of organic carbon estimated to be oxidized organic aerosol (OOA) from HR-TOF-AMS measurements was 73–100% modern.

Measurements of submicron particulate matter (PM) were performed at an urban background station, in Helsinki, Finland during wintertime to investigate the chemical characteristics and sources of PM1. The PM1 was dominated by sulfate and organics. The source apportionment indicated that organic aerosol (OA) was a mixture from local sources (biomass burning (BBOA), traffic, coffee roaster (CROA)), secondary compounds formed in local wintertime conditions (nitrogen containing OA (NOA), semivolatile oxygenated OA (SV-OOA), and regional and long-range transported compounds (low volatile oxygenated OA, LV-OOA). BBOA was dominated by the fragments C2H4O2 + and C3H4O2 + (m/z 60.021 and 73.029) from levoglucosan, or other similar sugar components, comprising on average 32% of the BBOA mass concentration. The ratio between fragments C2H4O2 +/C3H4O2 + was significantly lower for CROA (=1.1) when compared to BBOA (=2.1), indicating that they consisted of different sugar compounds. In addition, a component containing ...

A two weeks measurement campaign by a mobile laboratory van was performed at downtown Helsinki, Finland, in winter 2010. The characteristics of air pollutants such as fine particles in the size ranges of 7-40 nm (N_(p40)) and 40-1000 nm (N_(p1000)), black carbon (BC), fine particle mass (PM_(2.5)), as well as gaseous compounds NO, NO_2, NO_x, CO and CO_2 were studied. The statistical analysis showed that the air pollution conditions strongly depended on the traffic flow area; therefore, the street sections were classified as high traffic flow areas (HTF1-HTF4), low traffic flow areas (LTF1-LTF5), and urban background areas (BG1-BG3). Large variation of particle emissions was observed, and the momentary peak particle concentrations were 8 × 10^5 cm^(-3). At the HTF areas exhaust emissions followed clearly daily average heavy duty vehicle counts rather than the average daily vehicle counts. Higher correlation coefficients were found between CO_2 and NO than between CO_2 and N_(tot). The dispersion studies indicated that the air pollution conditions strongly improved from high traffic flow areas to low traffic flow areas. Therefore, proper city planning and locating, for example, cycle tracks, schools and hospitals farther from busy city streets might significantly reduce exposure risk for humans.

Atmospheric particulate matter samples (PM2.5 and PM10) were collected at urban sites (Sao Paulo, SPA; Piracicaba, PRB) in Sao Paulo State, Brazil. In order to characterize the chemical composition of particulate matter, several chemical components were analyzed from the samples, and among these were inorganic and organic anions, monosaccharide anhydrides, and organic and elemental carbon. Long-range transport of the particulate matter while sugar cane was being burned contributed to an increase in PM2.5 and PM10 concentrations at the SPA site. Sulphate, nitrate, ammonium, elemental carbon and particulate organic material (POM) were major components of the total PM2.5 and PM2.5-10. The contribution of POM to PM2.5 at PRB was 29%, similar to the results found for the winter season at the SPA site.The Cl^-/Na^+ ratio at the SPA site for PM2.5 was different from that at the other site, with chloride depletion indicating several sources beyond sea salt. The occurrence of levoglucosan and its correlations with potassium confirm the contribution of local biomass burning (at PRB) and long-range transported particles at SPA. OC/EC ratios and the correlation coefficients indicated secondary formation of OC at both sites.

Particle emissions affect radiative forcing in the atmosphere. Therefore, it is essential to know the physical and chemical characteristics of them. This work studied the chemical, physical, and optical characteristics of particle emissions from small-scale wood combustion, coal combustion of a heating and power plant, as well as heavy and light fuel oil combustion at a district heating station. Fine particle (PM1) emissions were the highest in wood combustion with a high fraction of absorbing material. The emissions were lowest from coal combustion mostly because of efficient cleaning techniques used at the power plant. The chemical composition of aerosols from coal and oil combustion included mostly ions and trace elements with a rather low fraction of absorbing material. The single scattering albedo and aerosol forcing efficiency showed that primary particles emitted from wood combustion and some cases of oil combustion would have a clear climate warming effect even over dark earth surfaces. Instead, coal combustion particle emissions had a cooling effect. Secondary processes in the atmosphere will further change the radiative properties of these emissions but are not considered in this study.

Heavy fuel oil (HFO) is a commonly used fuel in industrial heating and power generation and for large marine vessels. In this study, the fine particle emissions of a 47 MW oil-fired boiler were studied at 30 MW power and with three different fuels. The studied fuels were HFO, water emulsion of HFO, and water emulsion of HFO mixed with light fuel oil (LFO). With all the fuels, the boiler emitted considerable amounts of particles smaller than 200 nm in diameter. Further, these small particles were quite hygroscopic even as fresh and, in the case of HFO+LFO emulsion, the hygroscopic growth of the particles was dependent on particle size. The use of emulsions and the addition of LFO to the fuel had a reducing effect on the hygroscopic growth of particles. The use of emulsions lowered the sulfate content of the smallest particles but did not affect significantly the sulfate content of particles larger than 42 nm and, further, the addition of LFO considerably increased the black carbon content of particulate matter. The results indicate that even the fine particles emitted from HFO based combustion can have a significant effect on cloud formation, visibility, and air quality.

In this study the characteristics, sources and water-solubility of submicron organic aerosol (OA) were investigated in Helsinki, Finland. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to determine the submicron non-refractory aerosol components nitrate, sulfate, ammonium, chloride and organics between April 9 and May 8, 2009. The concentrations of the major water-soluble ions and water-soluble organic carbon (WSOC) were measured by a particle-into-liquid sampler (PILS) combined with a total organic carbon (TOC) analyzer and two ion chromatographs (IC) between April 25 and May 28, 2009. Parallel measurements of the submicron particulate matter (PM 1 ), organic carbon (OC), black carbon (BC), meteorological quantities and trace gases were used to complement and validate the AMS and PILS-TOC-IC data. Sources or atmospheric processes affecting the organic aerosol were investigated by applying the Positive Matrix Factorization (PMF) analysis to the high-resolution mass spectra of the HR-ToF-AMS organics. All together seven factors were needed to describe the variation in the obtained dataset. The factors consisted of two different types of low-volatility oxygenated OA (LV-OOA), local and long-range-transported (LRT) biomass burning OA (BBOA), semi-volatile OA (SV-OOA), hydrocarbon-like OA (HOA), and one local source (coffee roastery). These factors were interpretable and could be connected to specific sources or chemical characteristics (biomass burning, traffic, biogenic emissions, oxidized long-range-transported aerosols, marine-processed aerosols and nearby industrial activity) of ambient aerosols. In order to study the organic fraction and PMF factors further, the elemental ratios OM:OC, O:C, H:C and N:C were calculated. The value of the OM:OC ratio varied between 1.4 and 2.1. A high OM:OC ratio (1.5–2.1) was observed for the highly-oxidized and water-soluble fraction, whereas this ratio was clearly lower (1.2–1.4) for local and fresh sources such as traffic. Two different factors representing local and long-range-transported biomass burning were observed. Local biomass burning emissions had a lower OM:OC ratio, indicating that this factor was less aged and had a different source area compared with the LRT BBOA. The water-solubilities of the OA factors were studied by investigating the correlation between these factors and WSOC and by reconstructing the concentration of water-soluble particulate organic matter (WSPOM) from the OA factors. The reconstructed WSPOM had a good correlation with the measured concentration of WSPOM.

To assess the origin and transformation of carbonaceous material in the marine boundary layer of the Eastern Mediterranean, a total of 111 size segregated aerosol samples have been collected using a 12-stage Small-Deposit-area low-volume-Impactor (SDI) covering an almost 3 year period. The samples have been analyzed for organic (OC), elemental (EC), water-soluble organic carbon (WSOC) and ionic components. Maxima of OC, EC and WSOC mass size distributions were found in the accumulation mode (0.449 μm) with occasionally a minor, secondary peak in the coarse mode (2.68 μm). OC and WSOC concentrations peak during summertime due to photochemistry, while EC during autumn, and spring. In general, almost 2/3 of OC and EC concentrations are found in the PM 1 fraction of the aerosol with OC being mostly secondary and therefore highly oxidized and water-soluble to a great extent (∼70%). Using the EC-tracer method, it was found that 83 ± 11% of the PM 10 organic carbon is secondary, with the percentage reaching ∼70% for the PM 1 fraction, a value in very good accordance to WSOC/OC ratio. Ammonium sulfate accounts for 75.5 ± 21.7% and 9.3 ± 1.9% of the aerosol mass in the fine and coarse fraction respectively, exhibiting maximum concentrations also in the accumulation mode. It was estimated that, on average, sea salt and mineral dust account for 33% and 45% of the coarse inorganic mass fraction, respectively.

The aim of this study was to compare four alternatives for providing decentralized energy production in small communities in terms of their flue gas emissions and toxicological properties of the emissions. In this study, two different size classes of boilers were examined and the use of fossil fuel oils was compared against wood fuels. The lowest PM1 emission, 0.1 mg MJ−1, was observed from small-scale light fuel oil combustion. In medium-scale wood combustion, PM1 emission values from a grate fired wood combustion boiler (10 MW) without particulate filtration were the highest (264 mg MJ−1) but were substantially reduced down to 0.6 mg MJ−1 due to the usage of an electrostatic precipitator (ESP). The wood combustion particles were mainly formed of potassium salts. In light fuel oil combustion, one of the main components in the particles was sulphate whereas in heavy fuel oil combustion also significant amounts of V and Ni were emitted. Pellet combustion produced the lowest PAH emissions. Overall, oil combustion produced higher amount of PAHs than wood combustion. This was indicated also as a higher cytotoxicity of the oil combustion samples when compared to those from wood combustion in the corresponding scale of boilers. However, when calculated on an equal mass basis, the particles collected after ESP were even more cytotoxic which can be explained by the altered chemical characteristics of the emissions in the ESP. Due to the variation in the emissions and in the toxicity of the emissions, we propose that in the long term, not only the emission levels but also the toxicity of the emissions should be taken into account in the regulations of the emission limits of the combustion plants.

High time resolution chemical characterization of submicron particles was carried out in the South American city of Santiago de Chile using the Aerosol Chemical Speciation Monitor (ACSM). The instrumentation operated for 100 days from August 17 th to November 23 rd 2011 in an urban station located inside the University of Santiago de Chile (USACH) campus. In addition, a semi-continuous OC/EC analyzer was also run in parallel with the ACSM for some of this time. Meteorological conditions varied along the studied period due to the transition from winter to spring time. Atmospheric temperature inversions were responsible for hourly average sub-micron particulate matter levels of up to 80 μg/m 3 , especially during the night time. The average submicron particle mass concentration (± standard deviation) for the whole period was 29.8 ± 25 μg/m 3 . Aerosol particles were composed mainly of organics 59%, followed by nitrate, ammonium, sulfate, black carbon and chloride with contributions of 14, 12, 8, 3 and 3%, respectively. Using positive matrix factorization, the organic fraction was divided into four distinct types of organic aerosol representing fresh automobile exhaust, biomass burning, and two oxygenated organic aerosol factors with different oxidation states. The transition from winter to spring was clearly seen in the composition of OA. The emissions from primary sources, such as vehicle and biomass burning, decreased in the period leading to spring, whereas the amount of oxygenated organic aerosol increased over the same time. This study shows that high time resolution measurements of aerosol chemical composition can lead to better characterizations of the evolution and sources of pollutants in an urban atmosphere.

A measurement campaign by a mobile laboratory van was performed in urban microenvironments bounded by a busy street Mannerheimintie in the city center of Helsinki, Finland. The characteristics of spatiotemporally high-resolution pollutant concentrations were studied such as ultrafine particles in the size range of 3–414 nm, black carbon BC, fine particle mass PM2.5, as well as nitrogen oxides NO and NO2. In addition, the effects of street geometry and roadside structure on the local dispersion of traffic emissions were analyzed as well. Meteorological conditions stayed stable and the wind direction was perpendicular to Mannerheimintie during the campaign. The highest particle concentrations were ∼8 × 105 cm−3, of which around 94% was smaller than 40 nm. At the pavement, the average concentration was in maximum 5 × 104 cm−3; around 80% of the particles was smaller than 40 nm. The volatility fraction was 75% by number. Due to the street canyon effect by the surrounding buildings, the downwind concentrations were around 24% of the upwind concentrations for particle number, 28% of NO, 39% of BC and 70% of NO2 concentrations. Furthermore, the upwind concentrations were higher than the simultaneously measured concentrations within the traffic flow. In fact, the particle count was around 3-fold, BC 2.5-fold, PM2.5 and NO2 1.5-fold compared to the concentrations while driving. Thus, for this measurement site and under these meteorological conditions, the exposure to pedestrians and cyclist on the upwind pavement is even higher than the driver's exposure. If the downwind buildings were parallel to Mannerheimintie, the concentrations dropped significantly at the pavement and continued decreasing slightly in the courtyards. When the downwind buildings were perpendicular to Mannerheimintie, a gradual reduction in the concentrations between the buildings was observed. However, at a distance of approximately a hundred meters a parallel side street which was a street canyon, started to affect the concentrations resulting in an increased exposure risk for pedestrians and cyclists. Understanding the local transport and the dispersion of traffic emissions are important for city planning and air quality assessment.

The effect of fuel ethanol content (10 %, 85 %, 100 %) on primary emissions and on subsequent secondary aerosol formation was investigated for a EURO5 flex-fuel gasoline vehicle. Emissions were characterized during the New European Driving Cycle (NEDC) using a comprehensive setup of high time resolution instruments. Detailed chemical composition of exhaust particulate matter (PM) was studied using a soot particle aerosol mass spectrometer (SP-AMS) and secondary aerosol formation using a potential aerosol mass (PAM) chamber. For the primary gaseous compounds, an increase in total hydrocarbon emissions and a decrease of aromatic BTEX (benzene, toluene, ethylbenzene and xylenes) compounds was observed when the amount of ethanol in fuel increased. In regard to particles, largest primary particulate matter concentrations and potential to form secondary particles were measured for the E10 fuel (10 % ethanol). As the ethanol content of the fuel increased, a significant decrease in average primary particulate matter concentrations over the NEDC cycle was found, PM emissions being 0.45, 0.25 and 0.15 mg m−3 for E10, E85 and E100, respectively. Similarly, a clear decrease in secondary aerosol formation potential was observed with larger contribution of ethanol in fuel. Secondary to primary PM ratios were 13.4, and 1.5 for E10 and E85, respectively. For E100 a slight decrease in PM mass was observed after the PAM chamber, indicating that the PM produced by secondary aerosol formation was less than the PM lost via e.g. wall losses or degradation of POA in the chamber. For all fuel blends, the formed secondary aerosol consisted mostly of organic compounds. For E10 the contribution of organic compounds containing oxygen increased from 35 %, measured for primary organics, to 62 % after the PAM chamber. For E85 the contribution of organic compounds containing oxygen increased from 42 % (primary) to 57 % (after the PAM chamber), whereas for E100 the amount of oxidized organics remained the same (approximately 62 %) with the PAM chamber when compared to the primary emissions.

International audience; In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.

Atmospheric emissions, including particle number and size distribution, from a 726 MWth coal-fired power plant were studied experimentally from a power plant stack and flue-gas plume dispersing in the atmosphere. Experiments were conducted under two different flue-gas cleaning conditions. The results were utilized in a plume dispersion and dilution model taking into account particle formation precursor (H2SO4 resulted from the oxidation of emitted SO2) and assessment related to nucleation rates. The experiments showed that the primary emissions of particles and SO2 were effectively reduced by flue-gas desulfurization and fabric filters, especially the emissions of particles smaller than 200 nm in diameter. Primary pollutant concentrations reached background levels in 200–300 s. However, the atmospheric measurements indicated that new particles larger than 2.5 nm are formed in the flue-gas plume, even in the very early phases of atmospheric ageing. The effective number emission of nucleated particles were several orders of magnitude higher than the primary particle emission. Modelling studies indicate that regardless of continuing dilution of the flue gas, nucleation precursor (H2SO4 from SO2 oxidation) concentrations remain relatively constant. In addition, results indicate that flue-gas nucleation is more efficient than predicted by atmospheric aerosol modelling. In particular, the observation of the new particle formation with rather low flue-gas SO2 concentrations changes the current understanding of the air quality effects of coal combustion. The results can be used to evaluate optimal ways to achieve better air quality, particularly in polluted areas like India and China.

The applicability, methods and limitations of constrained peak-fitting on mass spectra of low mass resolving power (m/dm50 ~ 500) recorded with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) are explored. Calibration measurements as well as ambient data are used to exemplify the methods that should be applied to maximise data quality and assess confidence in peak-fitting results. Sensitivity analyses and basic peak fit metrics such as normalised ion separation are employed to demonstrate which peak-fitting analyses commonly performed in high-resolution aerosol mass spectrometry are appropriate to perform on spectra of this resolving power. Information on aerosol sulphate, nitrate, sodium chloride, methanesulphonic acid as well as semi-volatile metal species retrieved from these methods is evaluated. The constants in a commonly used formula for the estimation of the mass concentration of hydrocarbon-like organic aerosol may be refined based on peak-fitting results. Finally, application of a recently-published parameterisation for the estimation of carbon oxidation state to ToF-ACSM spectra is validated for a range of organic standards and its use demonstrated for ambient urban data.

Atmospheric emissions, including particle number and size distribution, of a 726 MWth coal-fired power plant were studied experimentally from power plant stack and from flue gas plume dispersing in the atmosphere. Experiments were conducted under two different flue gas cleaning conditions. The results were utilised in a plume dispersion and dilution modelling taking into account nucleation particle precursor (H2SO4 resulted from the oxidation of emitted SO2) formation and assessment related to nucleation rates. The experiments showed that the primary emissions of particles and SO2 were effectively reduced by flue gas desulphurization and fabric filters, especially the emissions of particles smaller than 200 nm in diameter. Primary pollutant concentrations reached background levels in 200–300 seconds. However, the atmospheric measurements indicated that new particles are formed in the flue gas plume, even in the very early phases of atmospheric ageing. The effective number emission of nucleated particles were several orders of magnitude higher than the primary particle emission. Modelling studies indicate that regardless of continuing dilution of the flue gas, nucleation precursor (H2SO4 from SO2 oxidation) concentrations remain relatively constant. In addition, flue gas nucleation is more efficient than natural atmospheric nucleation. Especially, the observation of the new particle formation with rather low flue gas SO2 concentrations changes the current understanding on the air quality effects of coal-combustion. The results can be used to evaluate the optimal ways to achieve better air quality particularly in polluted areas like India and China.